79970-16-4Relevant articles and documents
Sulfur-containing metal complexes. 12. Reactions of α-thio carbanions with carbene complexes of the type [M(CO)5{O(alkyl)Ar}] and with the carbyne [(η5-MeC5H4)Mn(CO) 2(CPh)][BCl4]
Raubenheimer, Helgard G.,Kruger, Gert J.,Lombard, Antonie Van A.,Linford, Lorna,Viljoen, Joey C.
, p. 275 - 284 (2008/10/08)
A series of pentacarbonyl thiocarbene complexes of chromium and tungsten such as [M(CO)5{C(Ph)-SCH=C(OR1)Ph}] [M = Cr, R1 = Me (8); M = W, R1 = Et (9)] can be prepared by reaction of Fischer-type carbene complexes with lithiothioacetals or derivatives thereof. The products that form indicate that the synthesis involves double nucleophilic attack of each lithio compound on two carbene centers. The same class of carbenes produces a group of structurally different thione complexes when it reacts with LiC(= S)NMe2 or LiC(=S)NPh2. Lithium diisopropylamide plays a decisive role in some of these transformations. Two of the resulting complexes, [Cr(CO)5{S=C(C6H4Ph-o)CH=C(Me)NHCHMe 2}] (18) and [W(CO)5-{S=C(NPh2)CH2NPh2}] (20), have been identified by X-ray crystallography. Reaction of the carbyne complex [(η5-MeC5H4)Mn(CO)2CPh][BF 4] with LiC(=S)NMe2 affords the compound [(η5-MeC5H4)Mn(CO)2{S= C(Ph)SCH2C(=S)NMe2}] (23) which has been completely characterized by X-ray crystallography. Treatment of the Fischer carbene [Cr(CO)5{C(OEt)Ph}] with LiC=N(C6H4)S-o furnishes upon subsequent alkylation a Lappert-type carbene complex, [Cr(CO)5CN(Et)(C6H4)S-o] (26). It can be prepared in higher yield by trapping of the free carbene in solution. The structures of the new complexes and the mechanisms of their formation are discussed. Crystal data for 18: CrC24H21NO5S, Mr = 487.49, monoclinic, space group C2/c, a = 13.76 (1) A?, b = 20.14 (1) A?, c = 17.92 (1) A?, β = 98.3 (1)°, U = 4916 A?3, Z = 8, Dcalcd = 1.32 g cm-3. Crystal data for 20: WC31H22N2O5S, Mr = 718.41, triclinic, space group P1, a = 14.20 (2) A?, b = 10.48 (2) A?, c = 9.92 (2) A?, α = 97.6 (1)°, β = 97.2 (1), γ = 93.8 (1)°, U = 1446 A?3, Z = 2, Dcalcd = 1.65 g cm-3. Crystal data for 23: MnC19H20NO2S3, Mr = 445.59, triclinic, space group P1, a = 14.62 (1) A?, b = 11.56 (1) A?, c = 6.51 (1) A?, α = 91.6 (1)°, β = 96.7 (1)°, γ = 108.8 (1)°, U = 1032 A?3, Z = 2, Dcalcd = 1.43 g cm-3.
