Reactivity of the Anionic Carbonyltrirhenium Cluster [Re3(µ-H)3(µ3-ampy)(CO)9]− − Synthesis of Neutral Phosphane and Alkenyl Derivatives

Effects of substituents on the formation of rhenium carbyne and η2-vinyl complexes from the reactions of ReH5(PMe2Ph)3 with terminal alkynes

“…appreciably higher than that for the formation of complex 27 (the precursor to the carbyne complex 17, a model complex for 6). The reaction profile again is consistent with the experimental observation that the reaction of ReH 5 (PMe 2 Ph) 3 with HCRCSiMe 3 in the presence of HCl produced the carbyne complex Re(RCCH 2 SiMe 3 )Cl 2 (PMe 2 Ph) 3 (6) and the Z 2 -vinyl complex Re(Z 2 -CH 2 CSiMe 3 )Cl 2 (PMe 2 Ph) 3 (7) in a 1 : 0.3 molar ratio.…”

“…It has been demonstrated that the ligand environments can have a dramatic effect on the outcome of the reactions. Reactions of rhenium hydride complexes such as ReH(CO) 5 , 1 ReH(CO) 5Àn (PMe 3 ) n (n = 2, 3, 4), 2 Cp 2 ReH, 3 CpRe(CO)(NO)H, 4 Re(Br)(H)(NO)(PR 3 ) 2 (R = Cy, i-Pr), 5 Re 3 -(m-OCH 2 CMe 3 ) 3 H(OCH 2 CMe 3 ) 5 , 6 [ReH 2 Cl(bpy)(PPh(OEt) 2 ) 3 ]BPh 4 7 and ReH 5 (PhP((CH 2 ) 3 PCy 2 ) 2 ) 8 with alkynes produce simple insertion products, namely, Z 1 -vinyl complexes. Reactions of [Re(Z 2 -H 2 )-(CO) 2 P 3 ] + (P = P(OEt) 3 , PPh(OEt) 2 or PPh 2 OEt) 9 with terminal alkynes give vinylidene complexes.…”

“…Reactions of ReH(Rpz)(HRpz)(NO)-(PPh 3 ) 2 10 and (PNPtBu)ReH 4 (PNPtBu = (tBu 2 PCH 2 SiMe 2 ) 2 N) 11 with terminal alkynes yield acetylide complexes. Reactions of ReH 4 (mq)(PPh 3 ) 2 (mq is the monoanion of 2-mercaptoquinoline) with alkynes in the presence of EPF 6 (E = H, Ph 3 C) form the hydridocarbyne species [ReH 2 (RCCH 2 R)(mq)(PPh 3 ) 2 ]PF 6 . 12 During our study on the reaction of ReH 5 (PMe 2 Ph) 3 (1) with terminal alkynes HCRCR, we found that the outcome of the reactions is also dependent on the substituents of the alkynes.…”

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“…74 Rhenium cluster carbonyl chemistry seems set to expand further following studies of the 2-NH 2 py (HL) derivative [Re 3 (m-H) 3 (m 3 -L)(CO) 9 ] 2 , which has been reacted with H + in the presence of phosphines to give [Re 3 (m-H) 2 (m 3 -L)(CO) 9 PR 3 ] (R = Ph, 4-MeC 6 H 4 ) or of alkynes to give [Re 3 (m 3 -H)(m 3 -L)(m-RCNCHRA)(CO) 9 ] (R = RA = Et, Ph; R = H, RA = Ph; R = Ph, RA = H). 75 Protonation of trans-[Re(CN) 2 (dppe) 2 ] 2 gave various results. HBF 4 gave trans-[Re(CN)(CNH)(dppe) 2 ], [NHEt 3 ] + gave trans-[Re(CNNHEt 2 ) 2 (dppe) 2 ] + and solvation resulted from methanol.…”