Synthesis and Ligand Substitution Reactions of a Mesitylphosphido-Bridged Platinum(II) Dimer
| Autor: | Michael B. Chapman, Klaus Eichele, Louise M. Liable-Sands, David S. Glueck, Arnold L. Rheingold, Glenn P. A. Yap, Igor V. Kourkine, Roderick E. Wasylishen |
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| Rok vydání: | 1996 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 35:1478-1485 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic951020i |
| Popis: | The stable primary phosphine complexes trans-M(PH(2)Mes)(2)Cl(2) (1, M = Pd; 2, M = Pt; Mes = 2,4,6-(t-Bu)(3)C(6)H(2)) were prepared from Pd(PhCN)(2)Cl(2) and K(2)PtCl(4), respectively. Reaction of Pt(COD)Cl(2) (COD = 1,5-cyclooctadiene) with less bulky arylphosphines gives the unstable cis-Pt(PH(2)Ar)(2)Cl(2) (3, Ar = Is = 2,4,6-(i-Pr)(3)C(6)H(2); 4, Ar = Mes = 2,4,6-Me(3)C(6)H(2)). Spontaneous dehydrochlorination of 4 or direct reaction of K(2)PtCl(4) with 2 equiv of PH(2)Mes gives the insoluble primary phosphido-bridged dimer [Pt(PH(2)Mes)(mgr;-PHMes)Cl](2) (5), which was characterized spectroscopically, including solid-state (31)P NMR studies. The reversible reaction of 5 with PH(2)Mes gives [Pt(PH(2)Mes)(2)(mgr;-PHMes)](2)[Cl](2) (6), while PEt(3) yields [Pt(PEt(3))(2)(mgr;-PHMes)](2)[Cl](2) (7), which on recrystallization forms [Pt(PEt(3))(mgr;-PHMes)Cl](2) (8). Complex 5 and PPh(3) afford [Pt(PPh(3))(mgr;-PHMes)Cl](2) (9). Addition of 1,2-bis(diphenylphosphino)ethane (dppe) to 5 gives the dicationic [Pt(dppe)(mgr;-PHMes)](2)[Cl](2) (10-Cl), which was also obtained as the tetrafluoroborate salt 10-BF(4)() by deprotonation of [Pt(dppe)(PH(2)Mes)Cl][BF(4)] (11) with Et(3)N or by reaction of [Pt(dppe)(mgr;-OH)](2)[BF(4)](2) with 2 equiv of PH(2)Mes. Complexes 8, 9, and 10-Cl.2CH(2)Cl(2).2H(2)O were characterized crystallographically. |
| Databáze: | OpenAIRE |
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