CHEMISTRY OF PI-COMPLEXES DERIVED FROM [(PH3P)2PT-(ETA-3-CH2CCPH)](O3SCF3) - INTERCONVERSION BETWEEN ETA-3-ALKOXOALLYL AND ETA-3-OXOALLYL COMPLEXES AND BETWEEN ETA-3-AMINOALLYL AND ETA-IMINOALLYL COMPLEXES

被引：17

作者：

BAIZE, MW ^{[1
]}

FURILLA, JL ^{[1
]}

WOJCICKI, A ^{[1
]}

机构：

[1] OHIO STATE UNIV,DEPT CHEM,COLUMBUS,OH 43210

来源：

INORGANICA CHIMICA ACTA | 1994年 / 223卷 / 1-2期

关键词：

PLATINUM COMPLEXES; ALKOXOALLYL COMPLEXES; ANIMOALLYL COMPLEXES;

D O I：

10.1016/0020-1693(94)03983-6

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The eta3-alkoxoallyl complexes of platinum (2a-c: R = Me (a), Et (b), i-Pr (c)) derived from [(Ph3P)2Pt(eta3-CH2CCPh)]+ (1) and ROH are dealkylated by OMe- to form the eta3-oxoallyl complex (Ph3P)2Pt(eta3-CH2C(O)CHPh) (3). Reactions of 3 with Et3O+ and (MeO)2SO2 regenerate the eta3-alkoxoallyl complexes 2a,b. Treatment of 1 with H2O affords binuclear [((Ph3P)2Pt(eta3-(CH2)(CHPh)C))2O]2+ (4), which is converted to 3 upon treatment with two equivalents of OMe-. The eta3-aminoallyl complexes [(Ph3P)2Pt(eta3-CH2C(NHR)CHPh)]+ (6), obtained from 1 and RNH2 (R = p-MeC6H4NH2, p-O2NC6H4NH2), react with LiPh to afford the eta3-iminoallyl complexes (Ph3P)2Pt(eta3-CH2C(NR)CHPh) (7). Complexes 7 are protonated by HBF4 and alkylated by (MeO)2SO2 to yield 6 and [(Ph3P)2Pt(eta3-CH2C(NRMe)CHPh)]+ (8), respectively. The complex [(Ph3P)2Pt(eta3-CH2C(NMe2)-CHPh)]+ (5) undergoes fluxional behavior at ambient temperatures in solution, and this behavior is ascribed to rotation about the C=NMe2 bond. The reported chemistry is rationalized by eta3-allyl and metallacyclic resonance hybrid properties of 2-8.

引用

页码：1 / 4

页数：4

共 14 条

[11] CATIONIC (ETA-3-ALLYLIC) (ETA-4-DIENE)-PALLADIUM AND (ETA-4-DIENE)-PLATINUM COMPLEXES [J].