TY - JOUR
T1 - Mixed-metal cluster chemistry. 31.(1) reactions of dimolybdenum-diiridium clusters with alkylidyne complexes
AU - Randles, Michael D.
AU - Dewhurst, Rian D.
AU - Cifuentes, Marie P.
AU - Humphrey, Mark G.
PY - 2012/4/9
Y1 - 2012/4/9
N2 - Reactions of the tetrahedral clusters Mo 2Ir 2(μ-CO) 3(CO) 7(η 5-L) 2 (L = C 5H 5, C 5HMe 4) with the molybdenum alkylidyne complex Mo(≡CC 6H 4OMe-4)(CO) 2{(N 2C 3H 3) 3BH- κ 3N,N′,N″} afford the pentanuclear clusters Mo 3Ir 2(μ 4-C)(μ 3-CC 6H 4OMe-4)(μ-O)(CO) 6{(N 2C 3H 3) 3BH-κ 3N,N′,N″} (η 5-C 5H 5) 2 (1; 62%) and Mo 3Ir 2(μ 3-CC 6H 4OMe-4) (μ 3-η 2-CO)(μ-CO)(CO) 6{(N 2C 3H 3) 3BH-κ 3N, N′,N″}(η 5-C 5Me 4H) 2 (2; 65%), respectively, while the reaction of Mo 2Ir 2(μ-CO) 3(CO) 7(η-C 5H 5) 2 with W(≡CC≡CSiMe 3)(CO) 2{(N 2C 3H 3) 3BH- κ 3N,N′,N″} yields the butterfly cluster Mo 2Ir 2(μ 4-η 2-SiMe 3C 2C≡W(CO) 2{(N 2C 3H 3) 3BH-κ 3N,N′,N″} )(μ-CO) 4(CO) 4(η 5-C 5H 5) 2 (3; 60%). The identities of 1-3 have been confirmed by single-crystal X-ray diffraction studies. Cluster 1 contains μ 4-carbido and μ-oxido ligands resulting from CO cleavage. Cluster 2, with sterically more encumbering tetramethylcyclopentadienyl ligands that arrest CO cleavage, possesses a μ 3-η 2-CO ligand with a weak CO bond (1.272(7), 1.257(7) Å). Cluster 2 could not be converted into an analogue of cluster 1. The reaction with alkyne is more facile than the reaction with alkylidyne; cluster 3 results from addition of the C≡C bond (rather than the W≡C bond) across the Mo-Mo vector.
AB - Reactions of the tetrahedral clusters Mo 2Ir 2(μ-CO) 3(CO) 7(η 5-L) 2 (L = C 5H 5, C 5HMe 4) with the molybdenum alkylidyne complex Mo(≡CC 6H 4OMe-4)(CO) 2{(N 2C 3H 3) 3BH- κ 3N,N′,N″} afford the pentanuclear clusters Mo 3Ir 2(μ 4-C)(μ 3-CC 6H 4OMe-4)(μ-O)(CO) 6{(N 2C 3H 3) 3BH-κ 3N,N′,N″} (η 5-C 5H 5) 2 (1; 62%) and Mo 3Ir 2(μ 3-CC 6H 4OMe-4) (μ 3-η 2-CO)(μ-CO)(CO) 6{(N 2C 3H 3) 3BH-κ 3N, N′,N″}(η 5-C 5Me 4H) 2 (2; 65%), respectively, while the reaction of Mo 2Ir 2(μ-CO) 3(CO) 7(η-C 5H 5) 2 with W(≡CC≡CSiMe 3)(CO) 2{(N 2C 3H 3) 3BH- κ 3N,N′,N″} yields the butterfly cluster Mo 2Ir 2(μ 4-η 2-SiMe 3C 2C≡W(CO) 2{(N 2C 3H 3) 3BH-κ 3N,N′,N″} )(μ-CO) 4(CO) 4(η 5-C 5H 5) 2 (3; 60%). The identities of 1-3 have been confirmed by single-crystal X-ray diffraction studies. Cluster 1 contains μ 4-carbido and μ-oxido ligands resulting from CO cleavage. Cluster 2, with sterically more encumbering tetramethylcyclopentadienyl ligands that arrest CO cleavage, possesses a μ 3-η 2-CO ligand with a weak CO bond (1.272(7), 1.257(7) Å). Cluster 2 could not be converted into an analogue of cluster 1. The reaction with alkyne is more facile than the reaction with alkylidyne; cluster 3 results from addition of the C≡C bond (rather than the W≡C bond) across the Mo-Mo vector.
UR - http://www.scopus.com/inward/record.url?scp=84859599060&partnerID=8YFLogxK
U2 - 10.1021/om201053s
DO - 10.1021/om201053s
M3 - Article
SN - 0276-7333
VL - 31
SP - 2582
EP - 2588
JO - Organometallics
JF - Organometallics
IS - 7
ER -