Preparation, structures and some reactions of novel diynyl complexes of iron and ruthenium

Abstract

Reactions between HC triple bond CC triple bond CSiMe3 and several ruthenium halide precursors have given the complexes Ru(C triple bond CC triple bond CSiMe3)(L2)Cp'[Cp'= Cp, L = CO (1), PPh3 (2); Cp' = Cp*, L2= dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-yl complexes Ru(C triple bond CC triple bond CH)(L2)Cp'[Cp'= Cp, L = PPh3 (5); Cp'= Cp*, L2 = dppe (6)]. Replacement of H in 5 or 6 with Au(PR3) groups was achieved in reactions with AuCl(PR3) in the presence of KN(SiMe3)2 to give Ru(C triple bond CC triple bond CAu(PR3)](L2)Cp'[Cp' = Cp, L = PPh3, R = Ph (7); Cp' = Cp*, L2= dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped [Cp(Ph3P)2Ru]C triple bond CC triple bond C[Ru(dppe)Cp*] (10) was obtained from Ru(C triple bond CC triple bond CH)(dppe)Cp* and RuCl(PPh3)2Cp. Single-crystal X-ray structural determinations of and are reported, with a comparative determination of the structure of Fe(C triple bond CC triple bond CSiMe3)(dppe)Cp* (4), and those of a fifth polymorph of [Ru(PPh3)2Cp]2(mu-C triple bond CC triple bond C) (12), and [Ru(dppe)Cp]2(mu-C triple bond CC triple bond C) (13).

Bis(acetylido) Complexes of Ruthenium(II) Bearing Monodentate Phosphane Ligands

“…Increased stability of the carbon-silicon bond in complexes bearing trimethylsilylacetylide ligands has been observed for other ruthenium complexes, [6,20,21] and has been attributed to either steric protection of the silyl group [6,[21][22][23] or an increase in the vinylidene character of the ligand brought about by the donor effects of the phosphane ligands. [6] Subsequently, cis/trans-Ru(CϵCH) 2 (PMe 3 ) 4 (8) was successfully synthesised by direct reaction of acetylene with cisRuMe 2 (PMe 3 ) 4 (Scheme 2).…”

Some complexes containing carbon chains end-capped with tungsten or ruthenium groups and tricobalt carbonyl clusters

“…Extension of the reaction to that between 3 and Ru-(C"CC"CH)(dppe)Cp* [15] afforded dark red crystalline {Cp*(dppe)Ru}C"CC"CC{Co 3 (l-dppm)(CO) 7 } (5), obtained in 39% yield, along with Co 3 {l 3 -CC(O)-NEt 2 }(l-dppm)(CO) 7 (6) which has been described elsewhere [12]. Complex 5 was characterised from its X-ray structure (Fig.…”

“…The compounds W(C"CC"CH)(CO) 3 Cp [21], Ru(C"CC"CH)(dppe)Cp* [15], Ru(C"CH)(PPh 3 ) 2 -Cp [16], Co 3 (l 3 -CBr)(CO) 9 [22] and Co 3 (l 3 -CBr)(ldppm)(CO) 7 [12] were made by the cited methods. …”

Syntheses and Structures of Buta-1,3-Diynyl Complexes from “on Complex” Cross-Coupling Reactions

“…The irreversibility of similar diynyl complexes has been noted on previous occasions, 18 and is likely due to intermolecular coupling of the generated diynyl radicals. 66,85 A general scheme on this oxidation dimerization process is depicted in Scheme 2.…”

“…Metal oligo/polyynyl M{(C≡C) n H}L x species have attracted significant interest over several decades, serving as scaffolds for the assembly of bi- [1][2][3][4][5][6][7][8][9][10][11][12][13] and poly-metallic [14][15][16][17][18][19][20][21][22][23][24][25][26] complexes, and as models and building blocks for metallomacrocycles, 15,[27][28][29] and metallo-polymers. [30][31][32][33][34][35] Detailed studies of the underlying electronic structure of this family of complexes have been undertaken, using a variety of computational and spectroscopic methods, often with a view to modelling the behavior of these prototypical molecular wires.…”