Addition of Cr(CO) 5 to the M( η2- S 2) moiety of Cp 2 M(S 2H (Cp′ = tBuC 5H 4 : M = Ta; Cp X = C 5Me 4Et: M = Nb) and crystal structures of Cp′ 2TaS 2H · [Cr(CO) 5] n ( n = 1, 2)

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Reaction of Cp′ 2TaS 2H (Cp′ = tBuC 5H 4) or Cp 2 xNbS 2H (Cp x = C 5Me 4Et) with an excess of Cr(CO) 5THF gives the adducts Cp′ 2TaS 2H · Cr(CO) 5 1, Cp′ 2TaS 2H · 2Cr(CO) 5 2, and Cp 2 xNbS 2H · Cr(CO) 5 3 respectively. 1 and 2 are separated by fractional crystallisation. The crystal structures show the Cr(CO) 5 fragment in 1 to be coordinated to the ‘outer’ sulfur, and in 2 both Cr(CO) 5 fragments are coordinated to each sulfur of the S 2 ligand in a trans fashion. In all cases approximate sp 3 hybridisation of the S atoms is observed. The new compounds are thermally labile and give CO-free, trinuclear compounds of the type Cp 4M 2S 4Cr upon heating their solutions.