The reaction of a cationic carbyne complex of manganese, [(η-C5H5)(CO)2Mn⋮CC6H5]BBr4 (1), with [(Ph3P)2N]2[Ru3(CO)11] (3) in THF at low temperature gave the heteronuclear trimetal bridging carbyne complex [MnRu2(μ-H)(μ-CO)2(μ3-CC6H5)(CO)6(η-C5H5)] (7). A cationic carbyne complex of rhenium, [(η-C5H5)(CO)2Re⋮CC6H5]BBr4 (2), reacts similarly with 3, affording the corresponding bridging carbyne complex [ReRu2(μ-H)(μ-CO)2(μ3-CC6H5)(CO)6(η-C5H5)] (8) and neutral Re−carbyne dimer [Re(CO)2(η-C5H5)(μ-CC6H5)]2 (9). The compound [(Ph3P)2N]2[Os3(CO)11] (4) only reacts with 1 to give the trimetal bridging carbyne complex [MnOs2(μ-H)(μ-CO)2(μ3-CC6H5)(CO)6(η-C5H5)] (10) and neutral Mn−carbyne dimer [Mn(CO)2(η-C5H5)(μ-CC6H5)]2 (11). [(Ph3P)2N]2[Fe4(CO)13] (5) also reacts with cationic carbyne complexes 1 and 2 to give the trimetal bridging carbyne complexes [MnFe2(μ-H)(μ-CO)2(μ3-CC6H5)(CO)6(η-C5H5)] (12) and [ReFe2(μ-H)(μ-CO)2(μ3-CC6H5)(CO)6(η-C5H5)] (13), respectively. Product 13, when treated with an excess of PPh3, gave the PPh3-substituted bridging carbyne complex [ReFe2(μ-H)(μ-CO)2(μ3-CC6H5)(CO)5(PPh3)(η-C5H5)] (14). In contrast to carbonylmetal anions 3−5, [Mo(η-C5H5)2(H)CO][Mn3(CO)9(μ-SC6H5)4] (6) reacts with 1 to produce not the analogous bridging carbyne complexes but rather the mercapto−carbene complex [(η-C5H5)(CO)2MnC(SC6H5)C6H5] (15) and the thiolato-bridged Mo−Mn carbonyl complex [Mo(η-C5H5)(CO)2(μ-SC6H5)2Mn(CO)3] (16), while the analogous reaction of 2 with 6 yields the mercaptocarbene complex [(η-C5H5)(CO)2ReC(SC6H5)C6H5] (17) and phenylcarbene complex [(η-C5H5)(CO)2ReC(H)C6H5] (18). The structures of 7, 9, 13, 14, and 16 have been established by X-ray diffraction studies.

The N+H 2 reaction has attracted a great deal of attention from both the experimental and the theoretical community, and most of the attention has been paid to the first excited state N( 2 D) atoms in collisions with hydrogen molecules and the scalar properties of the reaction. In this paper, we study the stereo dynamical properties and calculate the reaction cross sections of the N( 4 S) + H 2 (v=0, j=0, 2, 5, 10) → NH(X 3 Σ − ) + H using the quasi-classical trajectory (QCT) method on an accurate NH 2 potential energy surface (PES) reported by Poveda and Varandas [

2 (CO) 6 ] (18). Analogous iron-sulfur cluster bridging carbene complexes [Fe 2 (µ-CO)(µ-CAr)(CO) 2 (η 5 -C 5 H 5 ) 2 -(µ-S)(µ-SC 6 H 5 )Fe 2 (CO) 6 ] (19, Ar ) C 6 H 5 ; 20, Ar ) p-CH 3 C 6 H 4 ) can also be obtained by the reactions of diiron cationic carbyne complexes [Fe 2 (µ-CO)(µ-CAr)(CO) 2 (η 5 -C 5 H 5 ) 2 ]BBr 4 (7, Ar ) C 6 H 5 ; 8, Ar ) p-CH 3 C 6 H 4 ) with [(µ-SLi)(µ-SC 6 H 5 )Fe 2 (CO) 6 ]. The structures of complexes 9, 13, 16, and 18 have been established by X-ray crystallography.

The reactions of cationic carbyne complexes of manganese and rhenium, [η-C 5 H 5 (CO) 2 Mt CC 6 H 5 ]BBr 4 (1, M ) Mn; 2, M ) Re), with diiron anionic compoundsComplexes 1 and 2 also react with [MgBr][Fe 2 (µ-CO)(µ-SeC 2 H 5 )(CO) 6 ] (5) to produce [Fe 2 -(µ-SeC 2 H 5 ) 2 (CO) 6 ] (15) and dimetal bridging carbene complexes [MnFe{µ-C(SeC 2 H 5 )C 6 H 5 }-(CO) 5 (η-C 5 H 5 )] ( 17) and [ReFe{µ-C(SeC 2 H 5 )C 6 H 5 }(CO) 5 (η-C 5 H 5 )] ( 18), respectively. 2 reacts similarly with 16) and a Re-Fe bridging carbene complex [ReFe{µ-C(SeC 4 H 9 -n)C 6 H 5 }(CO) 5 (η-C 5 H 5 )] ( 19), while the analogous reaction of 1 with 6 produced an unexpected trimetal bridging carbyne complex [MnFe 2 (µ-H)(µ-CO) 2 (µ 3 -CC 6 H 5 )CO) 6 (η-C 5 H 5 )] (20). The structures of complexes 9, 10, 13, 18, and 20 have been established by X-ray diffraction studies.