The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes

Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoro...
Ausführliche Beschreibung

Gespeichert in:

Autor*in:	Khusi, Bongumusa B. [verfasserIn] Mambanda, Allen [verfasserIn] Jaganyi, Deogratius [verfasserIn]

Format:	E-Artikel
Sprache:	Englisch

Erschienen:	2015

Schlagwörter:	Pyrazole Pyrazole Ring Terpy Aqua Ligand TMTU

Übergeordnetes Werk:	Enthalten in: Transition metal chemistry - Dordrecht [u.a.] : Springer Science + Business Media B.V, 1975, 41(2015), 2 vom: 01. Dez., Seite 191-203
Übergeordnetes Werk:	volume:41 ; year:2015 ; number:2 ; day:01 ; month:12 ; pages:191-203

Links:	Volltext

DOI / URN:	10.1007/s11243-015-0011-6

Katalog-ID:	SPR01809936X

Internformat


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245	1	4	\|a The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes
264		1	\|c 2015
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520			\|a Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results.
650		4	\|a Pyrazole \|7 (dpeaa)DE-He213
650		4	\|a Pyrazole Ring \|7 (dpeaa)DE-He213
650		4	\|a Terpy \|7 (dpeaa)DE-He213
650		4	\|a Aqua Ligand \|7 (dpeaa)DE-He213
650		4	\|a TMTU \|7 (dpeaa)DE-He213
700	1		\|a Mambanda, Allen \|e verfasserin \|4 aut
700	1		\|a Jaganyi, Deogratius \|e verfasserin \|4 aut
773	0	8	\|i Enthalten in \|t Transition metal chemistry \|d Dordrecht [u.a.] : Springer Science + Business Media B.V, 1975 \|g 41(2015), 2 vom: 01. Dez., Seite 191-203 \|w (DE-627)306713632 \|w (DE-600)1501083-1 \|x 1572-901X \|7 nnns
773	1	8	\|g volume:41 \|g year:2015 \|g number:2 \|g day:01 \|g month:12 \|g pages:191-203
856	4	0	\|u https://dx.doi.org/10.1007/s11243-015-0011-6 \|z lizenzpflichtig \|3 Volltext
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912			\|a GBV_ILN_22
912			\|a GBV_ILN_23
912			\|a GBV_ILN_24
912			\|a GBV_ILN_31
912			\|a GBV_ILN_32
912			\|a GBV_ILN_39
912			\|a GBV_ILN_40
912			\|a GBV_ILN_60
912			\|a GBV_ILN_62
912			\|a GBV_ILN_63
912			\|a GBV_ILN_69
912			\|a GBV_ILN_70
912			\|a GBV_ILN_73
912			\|a GBV_ILN_74
912			\|a GBV_ILN_90
912			\|a GBV_ILN_95
912			\|a GBV_ILN_100
912			\|a GBV_ILN_105
912			\|a GBV_ILN_110
912			\|a GBV_ILN_120
912			\|a GBV_ILN_138
912			\|a GBV_ILN_150
912			\|a GBV_ILN_151
912			\|a GBV_ILN_152
912			\|a GBV_ILN_161
912			\|a GBV_ILN_170
912			\|a GBV_ILN_171
912			\|a GBV_ILN_187
912			\|a GBV_ILN_213
912			\|a GBV_ILN_224
912			\|a GBV_ILN_230
912			\|a GBV_ILN_250
912			\|a GBV_ILN_281
912			\|a GBV_ILN_285
912			\|a GBV_ILN_293
912			\|a GBV_ILN_370
912			\|a GBV_ILN_602
912			\|a GBV_ILN_636
912			\|a GBV_ILN_702
912			\|a GBV_ILN_2001
912			\|a GBV_ILN_2003
912			\|a GBV_ILN_2004
912			\|a GBV_ILN_2005
912			\|a GBV_ILN_2006
912			\|a GBV_ILN_2007
912			\|a GBV_ILN_2008
912			\|a GBV_ILN_2009
912			\|a GBV_ILN_2010
912			\|a GBV_ILN_2011
912			\|a GBV_ILN_2014
912			\|a GBV_ILN_2015
912			\|a GBV_ILN_2020
912			\|a GBV_ILN_2021
912			\|a GBV_ILN_2025
912			\|a GBV_ILN_2026
912			\|a GBV_ILN_2027
912			\|a GBV_ILN_2031
912			\|a GBV_ILN_2034
912			\|a GBV_ILN_2037
912			\|a GBV_ILN_2038
912			\|a GBV_ILN_2039
912			\|a GBV_ILN_2044
912			\|a GBV_ILN_2048
912			\|a GBV_ILN_2049
912			\|a GBV_ILN_2050
912			\|a GBV_ILN_2055
912			\|a GBV_ILN_2057
912			\|a GBV_ILN_2059
912			\|a GBV_ILN_2061
912			\|a GBV_ILN_2064
912			\|a GBV_ILN_2065
912			\|a GBV_ILN_2068
912			\|a GBV_ILN_2070
912			\|a GBV_ILN_2086
912			\|a GBV_ILN_2088
912			\|a GBV_ILN_2093
912			\|a GBV_ILN_2106
912			\|a GBV_ILN_2107
912			\|a GBV_ILN_2108
912			\|a GBV_ILN_2110
912			\|a GBV_ILN_2111
912			\|a GBV_ILN_2112
912			\|a GBV_ILN_2113
912			\|a GBV_ILN_2116
912			\|a GBV_ILN_2118
912			\|a GBV_ILN_2119
912			\|a GBV_ILN_2122
912			\|a GBV_ILN_2129
912			\|a GBV_ILN_2143
912			\|a GBV_ILN_2144
912			\|a GBV_ILN_2147
912			\|a GBV_ILN_2148
912			\|a GBV_ILN_2152
912			\|a GBV_ILN_2153
912			\|a GBV_ILN_2188
912			\|a GBV_ILN_2190
912			\|a GBV_ILN_2232
912			\|a GBV_ILN_2336
912			\|a GBV_ILN_2446
912			\|a GBV_ILN_2470
912			\|a GBV_ILN_2472
912			\|a GBV_ILN_2507
912			\|a GBV_ILN_2522
912			\|a GBV_ILN_2548
912			\|a GBV_ILN_4012
912			\|a GBV_ILN_4035
912			\|a GBV_ILN_4037
912			\|a GBV_ILN_4046
912			\|a GBV_ILN_4112
912			\|a GBV_ILN_4125
912			\|a GBV_ILN_4126
912			\|a GBV_ILN_4242
912			\|a GBV_ILN_4246
912			\|a GBV_ILN_4249
912			\|a GBV_ILN_4251
912			\|a GBV_ILN_4305
912			\|a GBV_ILN_4306
912			\|a GBV_ILN_4307
912			\|a GBV_ILN_4313
912			\|a GBV_ILN_4322
912			\|a GBV_ILN_4323
912			\|a GBV_ILN_4324
912			\|a GBV_ILN_4325
912			\|a GBV_ILN_4326
912			\|a GBV_ILN_4333
912			\|a GBV_ILN_4334
912			\|a GBV_ILN_4335
912			\|a GBV_ILN_4336
912			\|a GBV_ILN_4338
912			\|a GBV_ILN_4393
912			\|a GBV_ILN_4700
936	b	k	\|a 58.00 \|q ASE
951			\|a AR
952			\|d 41 \|j 2015 \|e 2 \|b 01 \|c 12 \|h 191-203

Indexfelder

author_variant	b b k bb bbk a m am d j dj
matchkey_str	article:1572901X:2015----::hrlosbttetiaiettnceaigiadnhsbtttooaulgns
hierarchy_sort_str	2015
bklnumber	58.00
publishDate	2015
allfields	10.1007/s11243-015-0011-6 doi (DE-627)SPR01809936X (SPR)s11243-015-0011-6-e DE-627 ger DE-627 rakwb eng 660 ASE 58.00 bkl Khusi, Bongumusa B. verfasserin aut The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes 2015 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results. Pyrazole (dpeaa)DE-He213 Pyrazole Ring (dpeaa)DE-He213 Terpy (dpeaa)DE-He213 Aqua Ligand (dpeaa)DE-He213 TMTU (dpeaa)DE-He213 Mambanda, Allen verfasserin aut Jaganyi, Deogratius verfasserin aut Enthalten in Transition metal chemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1975 41(2015), 2 vom: 01. Dez., Seite 191-203 (DE-627)306713632 (DE-600)1501083-1 1572-901X nnns volume:41 year:2015 number:2 day:01 month:12 pages:191-203 https://dx.doi.org/10.1007/s11243-015-0011-6 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 58.00 ASE AR 41 2015 2 01 12 191-203
spelling	10.1007/s11243-015-0011-6 doi (DE-627)SPR01809936X (SPR)s11243-015-0011-6-e DE-627 ger DE-627 rakwb eng 660 ASE 58.00 bkl Khusi, Bongumusa B. verfasserin aut The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes 2015 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results. Pyrazole (dpeaa)DE-He213 Pyrazole Ring (dpeaa)DE-He213 Terpy (dpeaa)DE-He213 Aqua Ligand (dpeaa)DE-He213 TMTU (dpeaa)DE-He213 Mambanda, Allen verfasserin aut Jaganyi, Deogratius verfasserin aut Enthalten in Transition metal chemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1975 41(2015), 2 vom: 01. Dez., Seite 191-203 (DE-627)306713632 (DE-600)1501083-1 1572-901X nnns volume:41 year:2015 number:2 day:01 month:12 pages:191-203 https://dx.doi.org/10.1007/s11243-015-0011-6 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 58.00 ASE AR 41 2015 2 01 12 191-203
allfields_unstemmed	10.1007/s11243-015-0011-6 doi (DE-627)SPR01809936X (SPR)s11243-015-0011-6-e DE-627 ger DE-627 rakwb eng 660 ASE 58.00 bkl Khusi, Bongumusa B. verfasserin aut The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes 2015 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results. Pyrazole (dpeaa)DE-He213 Pyrazole Ring (dpeaa)DE-He213 Terpy (dpeaa)DE-He213 Aqua Ligand (dpeaa)DE-He213 TMTU (dpeaa)DE-He213 Mambanda, Allen verfasserin aut Jaganyi, Deogratius verfasserin aut Enthalten in Transition metal chemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1975 41(2015), 2 vom: 01. Dez., Seite 191-203 (DE-627)306713632 (DE-600)1501083-1 1572-901X nnns volume:41 year:2015 number:2 day:01 month:12 pages:191-203 https://dx.doi.org/10.1007/s11243-015-0011-6 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 58.00 ASE AR 41 2015 2 01 12 191-203
allfieldsGer	10.1007/s11243-015-0011-6 doi (DE-627)SPR01809936X (SPR)s11243-015-0011-6-e DE-627 ger DE-627 rakwb eng 660 ASE 58.00 bkl Khusi, Bongumusa B. verfasserin aut The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes 2015 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results. Pyrazole (dpeaa)DE-He213 Pyrazole Ring (dpeaa)DE-He213 Terpy (dpeaa)DE-He213 Aqua Ligand (dpeaa)DE-He213 TMTU (dpeaa)DE-He213 Mambanda, Allen verfasserin aut Jaganyi, Deogratius verfasserin aut Enthalten in Transition metal chemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1975 41(2015), 2 vom: 01. Dez., Seite 191-203 (DE-627)306713632 (DE-600)1501083-1 1572-901X nnns volume:41 year:2015 number:2 day:01 month:12 pages:191-203 https://dx.doi.org/10.1007/s11243-015-0011-6 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 58.00 ASE AR 41 2015 2 01 12 191-203
allfieldsSound	10.1007/s11243-015-0011-6 doi (DE-627)SPR01809936X (SPR)s11243-015-0011-6-e DE-627 ger DE-627 rakwb eng 660 ASE 58.00 bkl Khusi, Bongumusa B. verfasserin aut The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes 2015 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results. Pyrazole (dpeaa)DE-He213 Pyrazole Ring (dpeaa)DE-He213 Terpy (dpeaa)DE-He213 Aqua Ligand (dpeaa)DE-He213 TMTU (dpeaa)DE-He213 Mambanda, Allen verfasserin aut Jaganyi, Deogratius verfasserin aut Enthalten in Transition metal chemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1975 41(2015), 2 vom: 01. Dez., Seite 191-203 (DE-627)306713632 (DE-600)1501083-1 1572-901X nnns volume:41 year:2015 number:2 day:01 month:12 pages:191-203 https://dx.doi.org/10.1007/s11243-015-0011-6 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-PHA GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 58.00 ASE AR 41 2015 2 01 12 191-203
language	English
source	Enthalten in Transition metal chemistry 41(2015), 2 vom: 01. Dez., Seite 191-203 volume:41 year:2015 number:2 day:01 month:12 pages:191-203
sourceStr	Enthalten in Transition metal chemistry 41(2015), 2 vom: 01. Dez., Seite 191-203 volume:41 year:2015 number:2 day:01 month:12 pages:191-203
format_phy_str_mv	Article
institution	findex.gbv.de
topic_facet	Pyrazole Pyrazole Ring Terpy Aqua Ligand TMTU
dewey-raw	660
isfreeaccess_bool	false
container_title	Transition metal chemistry
authorswithroles_txt_mv	Khusi, Bongumusa B. @@aut@@ Mambanda, Allen @@aut@@ Jaganyi, Deogratius @@aut@@
publishDateDaySort_date	2015-12-01T00:00:00Z
hierarchy_top_id	306713632
dewey-sort	3660
id	SPR01809936X
language_de	englisch
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The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. 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author	Khusi, Bongumusa B.
spellingShingle	Khusi, Bongumusa B. ddc 660 bkl 58.00 misc Pyrazole misc Pyrazole Ring misc Terpy misc Aqua Ligand misc TMTU The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes
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topic_title	660 ASE 58.00 bkl The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes Pyrazole (dpeaa)DE-He213 Pyrazole Ring (dpeaa)DE-He213 Terpy (dpeaa)DE-He213 Aqua Ligand (dpeaa)DE-He213 TMTU (dpeaa)DE-He213
topic	ddc 660 bkl 58.00 misc Pyrazole misc Pyrazole Ring misc Terpy misc Aqua Ligand misc TMTU
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title	The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes
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title_full	The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes
author_sort	Khusi, Bongumusa B.
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title_sort	role of substituents in a bidentate n,n-chelating ligand on the substitution of aqua ligands from mononuclear pt(ii) complexes
title_auth	The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes
abstract	Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results.
abstractGer	Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results.
abstract_unstemmed	Abstract The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(H2Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCH3Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}($ H_{2} $O)2]($ ClO_{4} $)2, [Pt(dCF3Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, %$ k_{{{\text{obs }}\left( {1/2} \right)}} %$, for the stepwise substitution of the first and second aqua ligands obeyed the rate law: %$ k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] %$. The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF3Py) > Pt(H2Py) > Pt(dCH3Py), while that of the second was Pt(H2Py) ≈ Pt(dCF3Py) > Pt(dCH3Py). Lower pKa values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results.
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container_issue	2
title_short	The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes
url	https://dx.doi.org/10.1007/s11243-015-0011-6
remote_bool	true
author2	Mambanda, Allen Jaganyi, Deogratius
author2Str	Mambanda, Allen Jaganyi, Deogratius
ppnlink	306713632
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isOA_txt	false
hochschulschrift_bool	false
doi_str	10.1007/s11243-015-0011-6
up_date	2024-07-03T17:21:26.595Z
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The role of substituents in a bidentate N,N-chelating ligand on the substitution of aqua ligands from mononuclear Pt(II) complexes

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