Direct photolytic route to trans-Cr(CO) < inf> 4 (AsPh < inf> 3 ) < inf> 2 and crystal structures of cis-Mo(CO) < inf> 4 (AsPh < inf> 3 ) < inf> 2 and cis-W(CO) < inf> 4 (AsPh < inf> 3 ) < inf> 2

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The preparation of trans-Cr(CO)4(AsPh3)2 is accomplished in reasonable yield by the direct photolysis of a solution of Cr(CO)6 and an excess of AsPh3 in heptane. The structures of cis-Mo(CO)4(AsPh3)2 and cis-W(CO)4(AsPh3)2 are reported. These are found to be isostructural and consist of distorted octahedral geometries with As-M-As angles of 102.56(2) and 102.62(2)° for M = Mo and W, respectively. The Mo-As distances of 2.6428(9) and 2.6489(9) Å are significantly longer than those in the W analogue at 2.6384(6) and 2.6361(6) Å. On the basis of a comparison to literature data, the AsPh3 ligands in these molecules can be described as extremely compressed. © 2001 Elsevier Science B.V.

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Inorganica Chimica Acta