Structure and reactivity of titanium/platinum and palladium heterobinuclear complexes with. mu. -methylene ligands

Journal Article · Wed Feb 15 00:00:00 EST 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00186a026· OSTI ID:5053422

Ozawa, Fumiyuki; Park, Joon Won; Mackenzie, P B; Schaefer, W P; Henling, L M; Grubbs, R H ^[1]

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1. California Institute of Technology, Pasadena (USA)

A series of titanium/platinum and palladium heterobinuclear {mu}-methylene complexes Cp{sub 2} TiCH{sub 2}MX(Me)L has been prepared: M = Pt, X = Cl, L = PMe{sub 3} (2b), PMe{sub 2}Ph (2c), PMePh{sub 2} (2d); M = Pt, X = Me, L = PMe{sub 2}Ph (2e, 2f); M = Pd, X = Cl, L = PMe{sub 3} (2g). The {mu}-CH{sub 2}/{mu}-Cl complex 2c crystallizes in the monoclinic system in space group P2{sub 1}/n (No. 14), with a = 13.249 (3) {angstrom}, b = 11.646 (3) {angstrom}, c = 14.542 (5) {angstrom}, {beta} = 114.45 (2){degree}, V = 2042.6 (10) {angstrom}{sup 3}, Z = 4, and density = 1.87 g cm{sup {minus}3}. The {mu}-CH{sub 2}/{mu}-CH{sub 3} analogue 2e is isostructural to 2c and also crystallizes in space group P2{sub 1}/n (No. 14) with a = 13.333 (4) {angstrom}, b = 11.686 (2) {angstrom}, c = 14.351 (2) {angstrom}, {beta} = 115.03 (2){degree}, V = 2026.0 (8) {angstrom}{sup 3}, Z = 4, and density = 1.82 g cm{sup {minus}3}. structural studies indicate the following: (1) the Ti-CH{sub 2} bond possesses residual double-bond character, (2) there is a dative Pt {yields} Ti interaction, which may be regarded as {pi} back-donation from the platinum atom to the Ti{double bond}CH{sub 2} group, and (3) the {mu}-CH{sub 3} group in 2e is bound to the titanium atom through a three-center, two-electron agostic bond. Complexes 2c and 2d react with tertiary phosphines to give Cp{sub 2}(Cl)TiCH{sub 2}Pt(Me)L{sub 2} species, which form {mu}-(C,O)-ketene complexes Cp{sub 2}(Cl)TiOC({double bond}CH{sub 2})Pt(Me)L{sub 2} upon carbonylation. The palladium complex 2g undergoes a reductive elimination reaction to give Cp{sub 2}Ti(Et)Cl and Pd{sup 0}PMe{sub 3} complexes. 31 refs., 3 figs., 5 tabs.

• OSTI ID: 5053422
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:4; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL PREPARATION
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
METHYLENE RADICALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PALLADIUM CHLORIDES
PALLADIUM COMPOUNDS
PLATINUM CHLORIDES
PLATINUM COMPOUNDS
RADICALS
SYNTHESIS
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS