TY - JOUR
T1 - Synthesis and Ligand Substitution Reactions of a Mesitylphosphido-Bridged Platmum(II) Dimer
AU - Kourkine, Igor V.
AU - Chapman, Michael B.
AU - Glueck, David S.
AU - Eichele, Klaus
AU - Wasylishen, Roderick E.
AU - Yap, Glenn P A
AU - Liable-Sands, Louise M.
AU - Rheingold, Arnold L.
PY - 1996
Y1 - 1996
N2 - The stable primary phosphine complexes trans-M(PH2Mes*)2Cl2 (1, M = Pd; 2, M = Pt; Mes* = 2,4,6-(t-Bu)3C6H2) were prepared from Pd(PhCN)2Cl2 and K2PtCl4, respectively. Reaction of Pt(COD)Cl2 (COD = 1,5-cyclooctadiene) with less bulky arylphosphines gives the unstable cis-Pt(PH2Ar)2Cl2 (3, Ar = Is = 2,4,6-(i- Pr)3C6H2; 4, Ar = Mes = 2,4,6-Me3C6H2). Spontaneous dehydrochlorination of 4 or direct reaction of K2PtCl4 with 2 equiv of PH2Mes gives the insoluble primary phosphido-bridged dimer [Pt(PH2Mes)(μ-PHMes)Cl2 (5), which was characterized spectroscopically, including solid-state 31P NMR studies. The reversible reaction of 5 with PH2Mes gives [Pt(PH2Mes)2(μ-PHMes)]2[Cl]2 (6), while PEt3 yields [Pt(PEt3)2(μ-PHMes)MCl]2 (7), which on recrystallization forms [Pt(PEt3)(μ-PHMes)Cl]2 (8). Complex 5 and PPh3 afford [Pt(PPh3)(μ-PHMes)Cl]2 (9). Addition of 1,2-bis(diphenylphosphino)ethane (dppe) to 5 gives the dicationic [Pt(dppe)(μ-PHMes)]2[Cl]22 (10-Cl), which was also obtained as the tetrafluoroborate salt 10-BF4 by deprotonation of [Pt(dppe)(PH2Mes)Cl]-[BF4] (11) with Et3N or by reaction of [Pt(dppe)(μ-OH)]2[BF4]2 with 2 equiv of PH2Mes. Complexes 8, 9, and 10-C1·2CH2Cl2·2H2O were characterized crystallographically.
AB - The stable primary phosphine complexes trans-M(PH2Mes*)2Cl2 (1, M = Pd; 2, M = Pt; Mes* = 2,4,6-(t-Bu)3C6H2) were prepared from Pd(PhCN)2Cl2 and K2PtCl4, respectively. Reaction of Pt(COD)Cl2 (COD = 1,5-cyclooctadiene) with less bulky arylphosphines gives the unstable cis-Pt(PH2Ar)2Cl2 (3, Ar = Is = 2,4,6-(i- Pr)3C6H2; 4, Ar = Mes = 2,4,6-Me3C6H2). Spontaneous dehydrochlorination of 4 or direct reaction of K2PtCl4 with 2 equiv of PH2Mes gives the insoluble primary phosphido-bridged dimer [Pt(PH2Mes)(μ-PHMes)Cl2 (5), which was characterized spectroscopically, including solid-state 31P NMR studies. The reversible reaction of 5 with PH2Mes gives [Pt(PH2Mes)2(μ-PHMes)]2[Cl]2 (6), while PEt3 yields [Pt(PEt3)2(μ-PHMes)MCl]2 (7), which on recrystallization forms [Pt(PEt3)(μ-PHMes)Cl]2 (8). Complex 5 and PPh3 afford [Pt(PPh3)(μ-PHMes)Cl]2 (9). Addition of 1,2-bis(diphenylphosphino)ethane (dppe) to 5 gives the dicationic [Pt(dppe)(μ-PHMes)]2[Cl]22 (10-Cl), which was also obtained as the tetrafluoroborate salt 10-BF4 by deprotonation of [Pt(dppe)(PH2Mes)Cl]-[BF4] (11) with Et3N or by reaction of [Pt(dppe)(μ-OH)]2[BF4]2 with 2 equiv of PH2Mes. Complexes 8, 9, and 10-C1·2CH2Cl2·2H2O were characterized crystallographically.
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U2 - 10.1021/ic951020i
DO - 10.1021/ic951020i
M3 - Article
C2 - 11666362
AN - SCOPUS:0000700564
SN - 0020-1669
VL - 35
SP - 1478
EP - 1485
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 6
ER -