Pentadiynylidyne and Pentacarbido Complexes

Abstract

The reaction of the halocarbyne [W(CBr)(CO) 2 -(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with trimethylsilyl-butadiyne,m ediated by [Pd(PPh 3 ) 4 ]a nd CuI, affords the first pentadiynylidyne complex [W( CC CC CSiMe 3 )(CO) 2 (Tp*)].Desilylation provides ageneral route to heterobimetallic pentacarbido complexes,i ncluding [(Tp*)-(CO) 2 W(m-C 5 )(PPh 3 ) 2 Ru(h-C 5 H 5 )] and [(Ph 3 P) 2 (CO)HIr{(m-C 5 )W(CO) 2 (Tp*)} 2 ].

Dimetallapoly‐yn‐diylidynes: LnM≡C−(C≡C)x−C≡MLn (x=0–4)

“…Recently,the first example of apentadiynylidyne complex [W(CCCCCSiMe 3 )(CO) 2 (Tp*)] (3)w as shown to serve through desilylation as ap recursor to pentacarbido-bridged bi-and polymetallic complexes. [15] With 3 and the previously reported propargylidyne [W( CC CSiMe 3 )(CO) 2 (Tp*)] (4) [16] [17] afforded WC 10 W (50 %y ield, Scheme 3, Table 1).…”

Pentadiynylidyne and Pentacarbido Complexes

“…Molecular structure of 2 in acrystal (ellipsoids set at 50 % probability,hydrogen atoms omitted, pyrazolyl rings simplified, one of two crystallographically independentmolecules shown). [17] Selected averaged bond lengths []and angles [8 8]for the two molecules:W 1-C1 1.855(5), Si1-C5 1.846(5), C1-C2 1.353 (7), C2-C3 1.215 (7), C3-C4 1.373 (7), C4-C5 1.208 (7);W 1-C1-C21 70.5(4), C1-C2-C3 176.6(6), C3-C4-C5 174.5(6), C4-C5-Si1 174.4(5). (5) 1.353 (7) 1.214 (7) 1.370 (7) 1.207 (7) [W]C 5 SiMe 3…”

“…Molecular structure of 5 in acrystal of 5·2 CH 2 Cl 2 (ellipsoids set at 50 %p robability,h ydrogen atoms and solvent omitted,p henyl and pyrazolyl groups simplified). [17] Selected bond lengths []and angles [8 8]: W1-C1 1.870(5), Ru1-C5 1.965(5), C1-C2 1.336 (7), C2-C3 1.234 (7), C3-C4 1.345 (7), C4-C5 1.232 (7);W1-C1-C21 75.8(4), C1-C2-C3 175.5 (5), C2-C3-C4 179.2(5), C3-C4-C5 175.1(5), C4-C5-Ru1 174.6-(4), P1-Ru-P2 101.29(4)8 8. . Molecular structure of 7 in acrystal of 7·4 CHCl 3 (ellipsoids set at 50 %p robability,h ydrogensa nd solvent molecules omitted, phenyl and Tp*ligands simplified).…”

“…Molecular structure of 7 in acrystal of 7·4 CHCl 3 (ellipsoids set at 50 %p robability,h ydrogensa nd solvent molecules omitted, phenyl and Tp*ligands simplified). [17] Selected bond lengths []and angles [8 8]: W1-C1 1.838(11), C1-C2 1.369 (14), C2-C3 1.210 (14), C3-C4 1.383(13), C4-C5 1.168 (14), Ir-C5 2.053(11); W1-C1-C21 70.2(9), C1-C2-C3 177.1(12), C2-C3-C4 176.7(12), C3-C4-C5 174.0(13), C4-C5-Ir1 175.0 (12).…”

Electronic Properties of Poly‐Yne Carbon Chains and Derivatives with Transition Metal End‐Groups

“…The last three decades have witnessed a stunning collection of works devoted to the syntheses and characterizations of the redox properties, molecular and electronic structures of a variety of π‐conjugated carbon‐containing units spanning two transition metal organometallic termini Much of the interest for these so‐called molecular organometallic wires has been prompted by the rich redox chemistry of the different metal termini which encompass several transition metal elements such as, non‐exhaustively, Cr, Mn, Fe, Co, Mo, Ru, W, Re, Os, Pt, and Au organometallic fragments . Additionally, the efficiency of diverse linkers allows to convey electronic and magnetic communication between the termini.…”