Chalcogen–acetylide interaction and unusual reactivity of coordinated acetylide with water: synthesis and characterisation of [(η5-C5R5)Fe3(CO)6(μ3-E)(μ3-ECCH2RI)] (R=H, Me; RI=Ph, Fc; E=S, Se) and [(η5-C5R5)MoFe2(CO)6(μ3-S)(μ-SCCH2Ph)] (R=H, Me)

Photolysis of a benzene solution containing [Fe3(CO)9(μ3-E)2] (E=S, Se), [(η5-C5R5)Fe(CO)2(C6-point triple bond; length half of m-dashCRI)] (R=H, Me; RI=Ph, Fc), H2O and Et3N results in formation of new metal clusters [(η5-C5R5)Fe3(CO)6(μ3-E)(μ3-ECCH2RI)] (R=H, RI=Ph, E=S 1 or Se 2; R=Me, RI=Ph, E=S 3 or Se 4; R=H, RI=Fc, E=S 5; R=Me, RI=Fc, E=S 6 or Se 7). Reaction of [Fe3(CO)9(μ3-S)2]with [(η5-C5R5)Mo(CO)3(C6-point triple bond; length half of m-dashCPh)] (R=H, Me), under same conditions, produces mixed-metal clusters [(η5-C5R5)MoFe2(CO)6(μ3-S)(μ-SCCH2Ph)] (R=H 8; R=Me 9). Compounds 1–9 have been characterised by IR and 1H and 13C-NMR spectroscopy. Structures of 1, 5 and 9 have been established crystallographically. A common feature in all these products is the formation of new C-chalcogen bond to give rise to a (ECCH2RI) ligand.© Elsevie

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

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

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 studies of monoacetylide species towards chalcogen-bridged mixed-metal clusters:: synthesis and characterisation of [(η<SUP>5</SUP>-C<SUB>5</SUB>H<SUB>5</SUB>)<SUB>2</SUB>Fe<SUB>2</SUB>RuM<SUB>2</SUB>(CO)<SUB>6</SUB>(μ<SUB>3</SUB>-E)<SUB>2</SUB>{μ<SUB>4</SUB>-CC(Ph)C(Ph)C}] (M=Mo, W; E=S, Se) and [(η<SUP>5</SUP>-C<SUB>5</SUB>H<SUB>5</SUB>)<SUB>2</SUB>Fe<SUB>2</SUB>Ru<SUB>2</SUB>M<SUB>2</SUB>(CO)9(μ<SUB>3</SUB>-E)<SUB>2</SUB>{μ-CCPh}<SUB>2</SUB>] (M=W, E=S, Se)

Thermolysis of a toluene solution containing [Fe2Ru(CO)9(μ3-E)2] (E=S or Se) and [(η5-C5H5)M(CO)3(C=CPh)] (M=Mo or W) results in coupling of monoacetylide ligands and formation of new mixed-metal clusters [(η5-C5H5)2Fe2RuM2(CO)6(μ3-E)2{μ4-CC(Ph)C(Ph)C}] (M=Mo, E=S 1 or Se 2; M=W, E=S 3 or Se 4) and [(η5-C5H5)2Fe2Ru2M2(CO)9(μ3-E)2{μ-CCPh}2] (M=W, E=S 5 or Se 6). Compounds 1-6 have been characterised by IR and 1H- and 13C-NMR spectroscopy. Structures of 1 and 5 have been established crystallographically. Compound 1 features a tail-to-tail type of coupling of two acetylide groups on a Fe2RuMoS2 core and compound 5 is a hexanuclear Fe-Ru-W mixed-metal cluster with two uncoupled acetylide groups

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