Reduction of phenylacetylene in (Tp prime (CO) sub 2 W(PhC sub 2 H))(BF sub 4 ) to form a. beta. -agostic methylphenylcarbene ligand

Journal Article · Wed Oct 24 00:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00178a068· OSTI ID:6130063

Feng, S G; White, P S; Templeton, J L ^[1]

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1. Univ. of North Carolina, Chapel Hill (USA)

Agostic bonds have proliferated since the first insightful review by Brookhart and Green in 1983. Numerous {alpha}-agostic carbenes, alternatively described as protonated carbynes, of both groups V{sup 3} and VI{sup 4} have been reported by Schrock and co-workers. The paradigm for olefin insertion and polymerization reactions involves {beta}-agostic alkyls. Four-electron-donor alkyne ligands, common for group VI, provide access to {eta}{sup 2}-vinyl ligands which are precursors to {beta}-agostic carbene products as reported here. Addition of a nucleophile (H{sup {minus}}, Me{sup {minus}}) to the terminal carbon of the phenylacetylene ligand in (Tp{prime}(CO){sub 2}W(PhC{triple bond}CH))(BF{sub 4})(Tp{prime} = hydridotris(3,5-dimethylpyrazolyl)borate) forms an {eta}{sup 2}-vinyl ligand which can be protonated to form an alkylphenylcarbene ligand. The agostic bond present in (Tp{prime}(CO){sub 2}W{double bond}C(Ph)CH{sub 2}R)(BF{sub 4}) (R = H, Me), described in detail below, complements the range of saturated and unsaturated agostic ligands represented.

• OSTI ID: 6130063
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:22; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020400* -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
ACETYLENE
ALKENES
ALKYNES
CARBENES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
LIGANDS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYMERIZATION
RADICALS
REDUCTION
SYNTHESIS