Facile Access to Transition‐Metal–Carbonyl Complexes with an Amidinate‐Stabilized Chlorosilylene Ligand

Abstract

Three transition-metal-carbonyl complexes [V(L)(CO)(3)(Cp)] (1), [Co(L)(CO)(Cp)] (2), and [Co(L(2))(CO)(3)](+)[CoCO)(4)](-) (3), each containing stable N-heterocyclic-chlorosilylene ligands (L; L=PhC(NtBu)(2)SiCl) were synthesized from [V(CO)(4)(Cp)], [Co(CO)(2)(Cp)], and Co(2)(CO)(8), respectively. Complexes 1-3 were characterized by NMR and IR spectroscopy, EI-MS spectrometry, and elemental analysis. The molecular structures of compounds 1-3 were determined by single-crystal X-ray diffraction.

Ring Opening and Bidentate Coordination of Amidinate Germylenes and Silylenes on Carbonyl Dicobalt Complexes: The Importance of a Slight Difference in Ligand Volume

“…d, 9w, 18 In addition, the presence of the very bulky HMDS group in 1 also seems to favor the formation of complex 7 because the transfer of one arm of the amidinate group to the TM relaxes the steric crowding exerted by the HMDS group over the nearby CO ligands, as indicated by a widening of the Co1‐Ge1‐N3 angle from 128.1(1) ° in 6 (structurally analogous to 4 ) to 138.81(6) ° in 7 . The importance of the HMDS group in this transformation is also supported by the fact that reactions of [Fe 2 (CO) 9 ], [Co 2 (CO) 8 ], [Mn 2 (CO) 10 ], and [Re 2 (CO) 10 ] with related amidinate‐tetrylenes having anionic groups smaller than HMDS do not afford derivatives containing bridging ligands, but products having monodentate M‐donor tetrylene ligands, such as [Fe{κ 1 Sn Sn( t Bu 2 bzam)Cl}(CO) 4 ],9p [Fe{κ 1 Si Si( t Bu 2 bzam)O t Bu}(CO) 4 ],9q [Co{κ 1 Si Si( t Bu 2 bzam)Cl} 2 (CO) 3 ][Co(CO) 4 ],9f [TM{κ 1 Si Si( t Bu 2 bzam)Cl} x (CO) 6− x ][TM(CO) 5 ] (TM=Mn, Re),9l and [TM{κ 1 Si Si( t Bu 2 bzam)NPh 2 } 2 (CO) 4 ][TM(CO) 5 ] (TM=Mn, Re) 9i…”

Crystal structure of tricarbonyl(N-diphenylphosphanyl-N,N′-diisopropyl-P-phenylphosphonous diamide-κ2P,P′)cobalt(I) tetracarbonylcobaltate(−I) toluene 0.25-solvate

“…For a similar, carbonyl-bridged dinuclear cobalt complex with this PNPNH ligand, see: Hansen et al (2013). Examples for structural reports of other Co I -Co ÀI ion-pair complexes can be found in Fellmann et al (1983), Bockman & Kochi (1989), Zhang et al (1994), Uehara et al (2005), van Rensburg et al (2007) and Azhakar et al (2012). Other transition metal complexes with this ligand are described in Aluri et al (2010) and Dulai et al (2011).…”

Silylated Group 14 Ylenes: An Emerging Class of Reactive Compounds

“…With synthetic routes to all classes of heavy tetrylene complexes of group 4 metallocenes established, the question arose of whether the used synthetic methods would also allow access to silylated tetrylene complexes of later transition metals. Although group 5 metals are actually considered quite similar to those of group 4, the number of known tetrylene complexes is very small 106,107. An attempt to employ the stannylene PEt 3 adduct 11 to obtain a tantalum stannylene complex was made by use of TaCl 5 /Mg in the presence of 11 /PEt 3 .…”