Synthesis and structure of (.eta.-C5H5)W(PPh3)(CO)(CSPh): transformation of a thiocarbonyl ligand into a carbyne ligand

Reactions of co-ordinated ligands. Part 39. The synthesis of carbyne complexes from alkyne molybdenum and tungsten cations; formation and crystal structures of [Mo(CCH2But){P(OMe)3}2(η-C5H5)] and [Mo{C(SiMe3)CH2}{P(OMe)3}2(η5-C9H7)]

“…CH=CHBu'), 5.69 (m, 1 H, C,H,), 5.49 (m, 2 H, C,H,), 5.33 [dt, 1 H, CH=CHBu', J(HH) 14, J(HP) 4.5], 3.48 (m,27 H,POMe), J(CP) 8.55,J(CP) 3.74],133.4 [dt,MoCHSHBu',J(CP) 44.68,J(CP) 7.811,128.0,110.8,88.2,77.2 (C,H,), 51.9 (POMe), 36.8 N.m.r. : 'H(C6D6), 6 7.13 (m, 4 H, C9H7), 6.85 (m, 1 H, 1.24 ( ~, 9 H, Bu'); 13C-{ 'H} (C,D,),6 153.1 [dt,MoCH=CHBu',(CMe,), 30.5 (chfe,); 31P-{1H} (C,D,),AB,Spin System,6,204.8,6,190.9 6.92 (AA'BB' multiplet,4 H,indenyl),5.82 [d,2 H,indenyl Synthesis of Carbonyl(q -cyclopen tadienyl)bis ( 3,3-dimethylbut-1 -yne)…”

Preparation of the isocyanide complexes trans-[ReCl(CNR)(dppe)2](R = Me or But) and their reactions with acid to give carbyne complexes. X-Ray crystal structure of trans-[ReCl(CNHMe)(dppe)2][BF4]

“…This was then filtered off and the solution was kept a t ca. Final atomic co-ordinates ( x lo4) with estimated standard deviations in parentheses X 1720.5( 7) 1282 (5) 3 388 (5) 1608( 5) 1568 (5) 2 366 ( 18) 3 516(21) 2 562 (16) 152( 21 The data crystal was obtained by addition of Et20 to a CH,CI, solution of (2, R = Me) and cooling a t 0 "C. It was roughly spherical of diameter ca. 0.2 mm and was sealed in a capillary tube.…”

“…This activation is similar to that also observed for dinitrogen itself l4 but clearly isocyanide is intrinsically more susceptible to electrophilic attack than is dinitrogen, because dinitrogen at this rhenium site is not attacked by protons.15 Other small molecules, such as CS, ligating electron-rich centres also form related carbyne complexes as a result of electrophilic attack. 16 Presumably a suitable combination of electronreleasing co-ligands is necessary to allow sufficient backbonding to promote electrophilic attack and not all dinitrogen binding sites will achieve it. We are extending our studies to define the limits of reactivity.…”

Electrophilic and nucleophilic reactions of the vinylidene complex [Cp(PMe3)2Ru:C:C(SMe)2]BF4 and its derivatives

“…[Ru=C=C(SMe)2]BF4 (1)* 5.48 1.47 (d, 10.56 138.03 (d, 18.97) 139.99 (d)c 2b6 95.74 20.37 (d, 37.62) 19.54 (d, 36.73) 30.86 (1) 18.07 (1) 141.21 (d, 18.91) 146.53 (d)d 36 96.45 19.93 (d, 33.82) 19.25 (d, 33.42) 31.33 (1) 20.64 (1) 17.68 (1)…”