Syntheses of olefin and acetylene complexes, [Ru(C5H5)(PMe3)2(un)]PF6

Cyclopentadienyl-ruthenium and -osmium chemistry. Part 20. Synthesis and X-ray structure of a cationic ruthenium–vinylidene complex, [Ru(CCHMe)(PMe3)2(η-C5H5)]PF6

“…We have also confirmed the preparation of a further example with R = Ph (3), which had been described earlier. 6 The first two complexes differ from vinylideneruthenium complexes obtained previously in their colour ; other examples have been pink to reddish purple. Their characterisation as vinylidene derivatives, rather than as qzalkyne complexes, finally rests on the structural study reported below.…”

“…In this area we were only partially successful, the &carbon being found at 6 127.4 in (1) and at 6 114.7 in (3); in neither case were we able to locate the or-carbon resonance below 6 400. For the methylacetylide complexes ( 4) and [Ru-(CXMe)(PPh3)2(q-C5H5) 1, the P-carbon resonates at 6 98.7 and 104.3, respectively, while for (9, (6), and [Ru(CsCPh)-(PPh3)2(q-C5H5)], it occurs at 6 123.0, 123.0, and 123.5, indicating that the chemical shift is dependent more on the acetylide substituent than on any possible differences in degree of back bonding from the metal into the acetylide moiety as a result of changes in tertiary phosphine, and hence electron density on the metal. Other features of the 13C n.m.r.…”

Vinylidene, acetylide, and carbene complexes from reactions of 2,5-dithiahex-3-yne (MeSC.tplbond.CSMe) with Cp(PMe3)2Ru+

“…[Cp(PMe3)2Ru=C=C(H)(SMe2)](BF4)2 (9). To a stirred solution of complex 6 (98 mg, 0.21 mmol) in 20 mL of CH3CN was added [Me30]BF4 (100 mg, 0.68 mmol).…”

“…Table III. Crystal and Data Collection Parameters for [Cp(PMe,)2Ru=C=C(H)(SMe2)](BF4)2 (9) formula fw space group a, Á b, Á c, A P2i/n 16.641 (2) 8.861 (1) 18.168 (12). To a stirred solution of 11a (33 mg, 0.065 mmol) in 10 mL of MeOH was added 1.3 mL of a 0.10 M solution of NaOMe (0.13 mmol) under N2.…”

“…Table V. Bond Distances (Á) and Angles (deg) for [Cp(PMe3)2Ru=C=C(H)(SMe2)](BF4)2 (9) Bond Distances (Á)…”