Three-centre, two-electron interactions in Pt(II) diphosphine complexes
This thesis describes the chemistry of compounds exhibiting three-centre, two-electron Pt...H...B or Pt...H...C (agostic) interactions. The metalla-borane and -carbaborane complexes are reviewed in which the metal centre interacts with the borane or carbaborane ligand via three centre, two-electron M...H...B bridge bonds. Mononuclear agostic complexes involving [alpha]-, [beta]-, and more distant C-H bonds are reviewed. The synthesis of the complexes [PtR[sub 2] (P-P)] [R = Me, Ch[sub 2]Bu[sup t], (P-P) = (C[sub 6]H[sub 11])[sub 2]P(CH[sub 2])[sub 3]P(C[sub 6]H[sub 11])[sub 2], Bu[sup t][sub 2]P(CH[sub 2])[sub n]PBu[sup t][sub 2], n = 2, 3; R = Me, (P-P) = o-[(Bu[sup t][sub 2]PCH[sub 2])[sub 2]C[sub 6]H[sub 4]])] are described which react with monocarbaborane acid (HCB[sub 11]H[sub 12]) in diethyl ether to afford [Pt(P-P) (closo)-CB[sub 11]H[sub 12]][CB[sub 11]-H[sub 12]]. The reactions of these complexes with CH[sub 3]CN, C[sub 5]H[sub 5]N, C[sub 2]H[sub 2] and PPh[sub 3] are described. The synthesis is described of [Pt(CH[sub 2] = CHBu[sup t]) (P-P)] [(P-P) = Bu[sub 2][sup t]P(CH[sub 2])[sub n]PBu[sup t][sub 2], n = 2, 3 and o-[(Bu[sup t][sub 2]P(CH[sub 2])[sub 2]C[sub 6]H[sub 4]]] and their reaction with HBF[sub 4]OMe[sub 2]. The reaction is reported of [Pt[sub 2]([mu]-H)[sub 2][Bu[sup t][sub 2]P(CH[sub 2])[sub 3]PBu[sup t][sub 2]][sub 2]] [BF[sub 4]][sub 2] with 2, 3, 3-trimethyl-1-butene and 2,3-dimethyl-2-butene. The synthesis and NMR studies are discussed of [PtR[Bu[sup t][sub 2]P(CH[sub 2])[sub 3]PBu[sup t][sub 2]]] [BF[sub 4]] (R = CH[sub 2]Ch[sub 2]COOMe, CH[sub 2]CH[sub 2]COMe, [eta][sup 3]-C[sub 3]H[sub 5]). Also reported is the protonation of [Pt(CH[sub 2] = CHSiMe[sub 3]) (Bu[sup t][sub 2]PCH[sub 2]C[sub 6]H[sub 4]CH[sub 2]PBu[sup t][sub 2])] with HBF[sub 4]OMe[sub 2] and the reaction of [Pt([eta][sup 3]-CH[sub 3]CHC[sub 6]H[sub 5]) [Bu[sup t][sub 2]P(CH[sub 2])[sub 3]PBu[sup t][sub 2]]] with vinyltrimethylsilane.
- Research Organization:
- Salford Univ. (United Kingdom)
- OSTI ID:
- 5525594
- Resource Relation:
- Other Information: Thesis (Ph.D.). Order No. BRD-98236
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
PHOSPHINES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
STRUCTURAL CHEMICAL ANALYSIS
PLATINUM COMPLEXES
BORANES
CHEMICAL BONDS
NUCLEAR MAGNETIC RESONANCE
ORGANOMETALLIC COMPOUNDS
X-RAY DIFFRACTION
BORON COMPOUNDS
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
HYDRIDES
HYDROGEN COMPOUNDS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
RESONANCE
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
664000 - Atomic & Molecular Physics- (1992-)