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The reactions of manganese carbonyl with the ditertiary phosphorus ligand bis(dipheny1phosphino)-methane, dpm, and its arsenic analogue, dam, have been investigated. The major products are of the types Mn2(CO),(L-L), [(L-L) = dpm or dam], Mnz(C0)6(dpm)z and Mn,(CO)s(dpm)2.Mn,(C0)5(dpm), displays a carbonyl stretch at the extremely low frequency of 1645 cm-l. It has been shown that the molecule contains a carbonyl group bridging between the manganese atoms in a previously unknown manner.

The crystal structure of [Pd(dppm) Br], (dppm = Ph,PCH,PPh2) shows that the palladium(1) atoms are directly metal-metal bonded and adopt an idealised square-planar stereochemistry.THE preparation of the complexes [Pd(dam)X], (dam = Ph,AsCH,AsPh,; X = C1, Br) and their establishment as compounds of palladium(1) was recently rep0rted.l By the action of dppm (Ph,PCH,PPh,) and the halogenocarbonyls Pd(C0)X we have now prepared similar complexes of the type [Pd(dppm)X], and the crystal structure of one o f these, [Pd(dppm)Br],, is reported here.Crystal data : C,,HMBr2P,Pd,, M = 1141, monoclinic, space group P2,/c; a = 13-661(4), b = 16.726(4), c = 21.442(6) A, = 106-00(4)" (h = 0.7107 A for Mo-K,); U = 4710 A3, 2 = 4, D, = 1-61 g ~m -~, p = 27-18 cm-l for Mo-K,.Crystals were obtained from a dichloromethane-hexane solution and the structure was solved by conventional heavy atom methods. Least-squares refinement with