Unusual Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with the Carbonylmetal Anions [Ir(CO)₄]^-and [Ru(CO)₄]^2-. Novel Route to Heteropolymetallic Bridging Carbyne Complexes

Abstract

The reaction of a cationic carbyne complex of manganese, [(η 5 -C 5 H 5 )(CO) 2 MntCC 6 H 5 ]BBr 4 (1), with [(Ph 3 P) 2 N][Ir(CO) 4 ] (3) in THF at low temperature gives a novel Mn 2 -Ir 2 mixedtetrametal bridging carbyne complex with µ and µ 3 bridging carbyne ligands, [Mn 2 Ir 2 (µ-CC 6 H 5 )(µ 3 -CC 6 H 5 )(µ-CO) 3 (CO) 3 (η 5 -C 5 H 5 ) 2 ] (5), and a related Mn 2 -Ir 2 mixed-tetranuclear cluster with a µ bridging carbene ligand and a µ 3 bridging carbyne ligand, [Mn 2 Ir 2 {µ-C(CO)-C 6 H 5 }(µ 3 -CC 6 H 5 )(µ-CO) 3 (CO) 4 (η 5 -C 5 H 5 ) 2 ] (6). A cationic carbyne complex of rhenium, [(η 5 -C 5 H 5 )(CO) 2 RetCC 6 H 5 ]BBr 4 (2), reacts similarly with 3 to afford the corresponding Re 2 -Ir 2 mixed-tetrametal cluster [Re 2 Ir 2 {µ-C(CO)C 6 H 5 }(µ 3 -CC 6 H 5 )(µ-CO) 3 (CO) 4 (η 5 -C 5 H 5 ) 2 ] (8) and a novel Re-Ir 2 mixed-trimetal bridging carbyne complex with an allyl ligand, [ReIr 2 (µ-η 1 :η 2 -C 3 H 5 )(µ 3 -CC 6 H 5 )(µ-CO) 2 (CO) 4 (η 5 -C 5 H 5 )] (7). The cationic carbyne complex 1 also reacts with the anionic compound Na 2 [Ru(CO) 4 ] (4) to give a heterotrimetal bridging carbyne complex with a µ-H ligand, [MnRu 2 (µ-H)(µ-CO) 2 (µ 3 -CC 6 H 5 )(CO) 6 (η 5 -C 5 H 5 )] ( 10), and the manganese aminocarbene complex [(η 5 -C 5 H 5 )(CO) 2 MndC(C 6 H 5 )NH 2 ] (11), while the analogous reaction of the cationic carbyne complex 2 with 4 produces a novel Re 2 -Ru 2 mixed-tetrametal cluster with a µ 3 -C(CC 6 H 5 )(µ-CC 6 H 5 ) bridging carbene ligand, [Re 2 Ru 2 {µ 3 -C(CC 6 H 5 )(µ-CC 6 H 5 )}(µ-CO)(CO) 8 (η 5 -C 5 H 5 ) 2 ] (13), in addition to the corresponding heterotrimetal bridging carbyne complex [ReRu 2 (µ 3 -CC 6 H 5 )(µ-H)(µ-CO) 2 (CO) 6 (η 5 -C 5 H 5 )] ( 12) and aminocarbene complex [η 5 -C 5 H 5 (CO) 2 RedC(C 6 H 5 )NH 2 ] (14). The structures of complexes 6, 7, 11, 13, and 14 have been established by X-ray diffraction studies.

Activation of boryl-, borylene and metalloborylene complexes by isonitriles

“…The Mn-C1 bond in 4 (1.975(2) Å) is slightly shorter than the Mn-C NHC distances observed in manganese NHC complexes of the form [(Z 5 -C 5 H 5 )(OC) 2 Mn(NHC)] (2.002(2)-2.018(3) Å), 22 and longer than the MQC bonds found in typical Fischer-type carbene complexes of Mn (1.901(3)-1.955(5) Å). [35][36][37][38] The B1-N1 and B1-C1 distances in 4 are longer than those observed in 2 (Table 1), likely due to the increased electron density at boron supplied by strong s-donation from IMe. The C1-N1 bond length of 1.294(2) Å in 4 is very similar to that observed in 2 (1.290(2) Å), in the range of a CQN double bond.…”

Transition‐Metal‐Mediated Cleavage of C−C Bonds in Aromatic Rings

“…An intriguing CÀCs cission occurs upon mixing carbyne rhenium complex 37 with iridium carbonylate 38 (Scheme 25). The reactionl eads to two Re-Ir clusters, one of which (39)h as an allyl ligand presumably inherited from the cleavedC p. [56] Alternatively,t he allyl fragment could also be formed from phenylg roups of BPh 4 À or (Ph 3 P)N + ions. These scenarios might potentially be distinguished throughi sotope labeling studies.…”

Selective transformations of cyclopentadienyl ligands of transition-metal and rare-earth metal complexes

“…112), affording mixed-tetrametal cluster 113 and an unexpected mixed-trimetal bridging carbyne complex 114 containing an allyl ligand (Scheme 37). 66 For 114, the allyl group (C 3 H 5 ) presumably comes from the cyclopentadienyl ligand of 111.…”