A Base-Stabilized Silylene with a Tricoordinate Silicon Atom as a Ligand for a Metal Complex

Abstract

Treatment of base stabilized silylene [PhC(NtBu)(2)]SiOtBu (1) with a tricoordinate silicon atom and diiron nonacarbonyl [Fe(2)(CO)(9)] in tetrahydrofuran led to the formation of {[PhC(NtBu)(2)]SiOtBu}Fe(CO)(4) (2), the first stable metal complex derived from a base-stabilized tricoordinate silylene ligand. The solid-state structure and bonding situation of 2 were investigated with single-crystal X-ray diffraction and quantum chemical calculations.

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…”

Monomer versus Alcohol Activation in the 4‐Dimethylaminopyridine‐Catalyzed Ring‐Opening Polymerization of Lactide and Lactic O‐Carboxylic Anhydride

“…Therefore, [PhC(N t Bu) 2 ]SnCl and nonacarbonyldiiron [Fe 2 (CO) 9 ] were selected as probes to investigate their reaction behavior. The synthetic procedureof 5 (Scheme ) is similar to that of {[PhC(N t Bu) 2 ]SiO t Bu}Fe(CO) 4 28b…”

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

“…The first stable silylene was developed by using a chelating dianionic N‐donor substituent that forms a five‐membered ring with silicon(II), in an analogous fashion to Arduengo's N‐heterocyclic carbene . In recent years, stable silylenes have also been isolated with a range of monoanionic, bidentate N‐donor substituents such as (bis)amidinato, (bis)guanidinato, and β‐diketiminates . Furthermore, a free silicon(II) anion has recently been afforded by cleavage of one pyrazolyl from a tetrapyrazolyl silane, which has been coordinated to transition metals such as Pd, Pt, and Cu, demonstrating the use of electron‐withdrawing heterocyclic substituents to stabilize novel low‐valent silicon chemistry.…”