Three-centre, two-electron interactions in Pt(II) diphosphine complexes

Thesis/Dissertation · Wed Jan 01 04:00:00 EST 1992

OSTI ID:5525594

Mhinzi, G S

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
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
664000 -- Atomic & Molecular Physics-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
BORANES
BORON COMPOUNDS
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
HYDRIDES
HYDROGEN COMPOUNDS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PLATINUM COMPLEXES
RESONANCE
SCATTERING
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION