Reactivity of metal acetylides with chalcogen-bridged metal carbonyl cluster in presence of free alkyne molecule: synthesis and characterisation of [(η5-C5Me5)MFe3(μ3-S){(μ3-C(H)=C(R)S}(CO)6(μ3-CCPh)] (R=Ph, n-Bu and M=W, Mo) and [(η5-C5Me5)MFe3(μ3-S){(μ3-C(Fc)=C(H)S}(CO)7(μ3-CCPh)] (M=W, Mo)

Photolysis of benzene solution of [Fe3(CO)9(μ3-S)2] (1), [(η5-C5Me5)M(CO)3(C≡CPh)] (2a: M=W, 2b: M=Mo) and HC≡CR (3a: R=Ph, 3b: R=n-Bu, 3c: R={(η5-C5H5)(η5-C5H4)Fe}(Fc) yields two types of clusters: [(η5-C5Me5)MFe3(μ3-S){(μ3-C(H)=C(R)S}(CO)6(μ3-CCPh)] (4: M=W, R=Ph; 5: M=Mo, R=Ph: 6: M=W, R=n -Bu; 7: M=Mo, R=n-Bu) and [(η5-C5Me5)MFe3(μ3-S){(μ3-C(Fc)=C(H)S}(CO)7(μ3-CCPh)] (8: M=W; 9: M=Mo) featuring new C–S bond formation. The formation of 8 and 9 involve an unusual head to tail flip of the coordinated acetylide group. All compounds have been characterised by IR and 1H- and 13C-NMR spectroscopy. The structures of 5 and 8 have been established by X-ray crystallography.© Elsevie

Insertion of CS<SUB>2</SUB> into a metal acetylide bond and conversion of the bonding mode of S<SUB>2</SUB>CC&#8801;CPh from &#951;<SUP>2</SUP> to &#951;<SUP>3</SUP>

Photolysis of a benzene solution containing [(L)Mo(CO)3(C&#8801;CPh)] (L=&#951;5-C5H5 1; &#951;5-C5Me5 2) and CS2 leads to the formation of dithiopropiolato containing complexes, [(L)Mo(CO)2(&#951;2-S2CC&#8801;CPh)] (L=&#951;5-C5H5 4; L=&#951;5-C5Me5 5). In presence of air, [(&#951;5-C5H5)Mo(CO)3(C&#8801;CPh)] reacts with CS2 to give 4 as the major and [(&#951;5-C5H5)Mo(O)(&#951;3-S2CC&#8801;CPh)] (6) as minor products. Similarly, [(&#951;5-C5Me5)Mo(CO)3(C&#8801;CPh)] reacts with CS2 under aerobic conditions to give compound 5 along with [(&#951;5-C5Me5)Mo(O)(&#951;3-S2CC&#8801;CPh)] (7) as minor product. When solutions of 4 or 5 are photolysed under a constant purge of air, 4 gives 6, and 5 gives 7 in high yields. Room temperature stirring of 5 with [W(CO)5(THF)] forms [&#951;5-C5Me5)Mo(CO)2CS2{W(CO)5}2C&#8801;CPh] (9). All new compounds have been characterised by IR and 1H-NMR spectroscopy and the structures of 4, 6, 7 and 9 have been established crystallographically

Reactivity of metal acetylides with chalcogen-bridged metal carbonyl cluster in presence of free alkyne molecule: synthesis and characterisation of [(η<SUP>5</SUP>-C<SUB>5</SUB>Me<SUB>5</SUB>)MFe<SUB>3</SUB>(μ<SUB>3</SUB>-S){μ<SUB>3</SUB>-C(H):C(R)S}(CO)<SUB>6</SUB>(μ<SUB>3</SUB>-CCPh)] (R=Ph, n-Bu and M=W, Mo) and [(η<SUP>5</SUP>-C<SUB>5</SUB>Me<SUB>5</SUB>)MFe<SUB>3</SUB>(μ<SUB>3</SUB>-S){μ<SUB>3</SUB>-C(Fc):C(H)S}(CO)<SUB>7</SUB>(μ<SUB>3</SUB>-CCPh)] (M=W, Mo)

Photolysis of benzene solution of [Fe3(CO)9(μ3-S)2] (1), [(η5-C5Me5)M(CO)3(C≡CPh)] (2a: M=W, 2b: M=Mo) and HC≡CR (3a: R=Ph, 3b: R=n-Bu, 3c: R={(η5-C5H5)(η5-C5H4)Fe}(Fc) yields two types of clusters: [(η5-C5Me5)MFe3(μ3-S){(μ3-C(H)=C(R)S}(CO)6(μ3-CCPh)] (4: M=W, R=Ph; 5: M=Mo, R=Ph: 6: M=W, R=n -Bu; 7: M=Mo, R=n-Bu) and [(η5-C5Me5)MFe3(μ3-S){(μ3-C(Fc)=C(H)S}(CO)7(μ3-CCPh)] (8: M=W; 9: M=Mo) featuring new C-S bond formation. The formation of 8 and 9 involve an unusual head to tail flip of the coordinated acetylide group. All compounds have been characterised by IR and 1H- and 13C-NMR spectroscopy. The structures of 5 and 8 have been established by X-ray crystallography

Synthesis and characterization of ferrocenylchalcogenopropargyl complexes [Fe(&#951;<SUP>5</SUP>-C<SUB>5</SUB>H<SUB>4</SUB>E<SUP>I</SUP>CH<SUB>2</SUB>C&#8801;CH)<SUB>2</SUB>] (E<SUP>I</SUP> = Se, S) and their reactions to form unusual ferrocenyl-containing metal clusters with eclipsed Cp rings and new five-membered FeE<SUP>I</SUP>CHC=CH<SUB>2</SUB> ring ligand system

The new bis(chalcogenopropargyl)ferrocene complexes [Fe(&#951;5-C5H4EICH2C&#8801;CH)2] (EI = Se, 1; EI = S, 2) have been prepared by treatment of the dilithiated [Fe(&#951;5-C5H4Li)2] with Se or S powder, followed by reaction with propargyl bromide. Reaction of 1 and 2 with [Fe2M(&#956;3-E)2(CO)9] (E = S, Se and M = Fe, Ru) forms new clusters which feature an unusual five-membered FeEICHC=CH2 ring with a &#960; bond between the olefinic unit and the Fe atom, and the Cp rings adopt an eclipsed arrangement. The structures of 1 and [Fe(&#951;5-C5H4EICH2C&#8801;CH)(&#951;5-C5H4{Fe2M(CO)8(&#956;-E)(&#956;3-E)(EICHCCH2)})] (M = Fe, E = Se, EI = Se, 3; M = Fe, E = S, EI = Se, 4; M = Ru, E = S, EI = Se, 7) have been determined crystallographically