Structure and stereodynamics of [m(CO)5{P(C6H 4Me-o)3}] (M = Cr, Mo or W) and [cr(CO) 3{P(C6H4Me-o)3}]

James A.S. Howell, Paul C. Yates, Michael G. Palin, Patrick McArdle, Desmond Cunningham, Zeev Goldschmidt, Hugo E. Gottlieb, Daphna Hezroni-Langerman

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Abstract

The crystal structure of [Cr(CO)5{P(C6H 4Me-o)3}] has been determined. It reveals an exo 2 conformation for the phosphine ligand, in agreement with molecular mechanics calculations. Barriers to P-C rotation in the series [M(CO) 5{P(C6H4Me-o)3}] (M = Cr, Mo or W) are in the range 36-42 kJ mol-1; restricted M-P rotation is also evident in the low-temperature 13CO NMR spectrum of [Cr(CO) 5{P(C6H4Me-o)3}]. The crystal structure of the π complex [Cr(CO)3{P(C6H 4Me-o)}3] is most consistent with an electron-acceptor character for the P(C6H4Me-o)2 substituent. Crystal data: [Cr(CO)5{P(C6H4Me-o) 3}], monoclinic, space group P21/n, a = 10.774(2), b = 14.951(5), c = 14.687(7) Å, β = 91.45(2)°, Z = 4, R′ = 0.0980 for 209 variable parameters and 2326 observed reflections; [Cr(CO) 3{P(C6H4Me-o)3}], monoclinic, space group P21/a, a = 16.725(2), b = 7.340(1), c = 17.675(4), β = 92.66(2)°, Z = 4, R′ = 0.1187 for 263 variable parameters and 1848 observed reflections.

Original languageEnglish
Pages (from-to)2775-2780
Number of pages6
JournalJournal of the Chemical Society. Dalton Transactions
Issue number18
DOIs
StatePublished - 1993

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