Syntheses of Group 7 Metal Carbonyl Complexes with a Stable N-Heterocyclic Chlorosilylene

Abstract

Two structurally characterized manganese [L(2)Mn(CO)(4)](+)[Mn(CO)(5)](-) (1) and rhenium [L(3)Re(CO)(3)](+)[ReCO)(5)](-) (2) silylene complexes were prepared in one pot syntheses by reacting 1 equivalent of Mn(2)(CO)(10) with 2 equivalents of stable N-heterocyclic chlorosilylene L {L = PhC(NtBu)(2)SiCl} and 1 equivalent of Re(2)(CO)(10) with 3 equivalents of L in toluene at room temperature. Both complexes 1 and 2 were characterized by single-crystal X-ray structural analysis, NMR and IR spectroscopy, EI-MS spectrometry, and elemental analysis.

An Iminophosphonamido‐Chlorosilylene as a Strong σ‐Donating NHSi Ligand: Synthesis and Coordination Chemistry

“…In the case of ADSi D , a similar reaction with 1/6 of an equivalent of [RhCl(cod)] 2 in toluene leads to the formation of tris(ADSi) Rh I complex 10 , which shows three sharp signals in its 1 H NMR spectrum due to t Bu protons ( δ =1.52, 1.54, and 1.57 ppm) (Scheme 6). [16] The 29 Si NMR spectrum of 10 displays three doublets at δ =40.0 ( 1 J Si‐Rh =92.1 Hz), 40.1 ( 1 J Si‐Rh =114.1 Hz), 40.3 ppm ( 1 J Si‐Rh =94.5 Hz) with 103 Rh couplings, which is comparable to the spectrum of cationic silylene‐rhenium complex [(ADSi) 3 Re(CO) 3 ] + [ReCO) 5 ] − ( δ =40.3 and 47.4 ppm) [17] . The chloride elimination from 10 to yield the doubly bonded silylene complex did not occur due to the reduced electron density on the rhodium atom by the coordination of ligand D , which is a weaker electron donor than NHSi 1 .…”

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…”

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

“…Recently, we reported the high‐yielding synthesis of stable N‐heterocyclic chlorosilylene, L ( L =PhC(N t Bu) 2 SiCl), using lithium bis(trimethylsilyl)amide as a dehydrochlorinating agent 8. As part of our ongoing research program, we are investigating the reactivity of chlorosilylene L with other substrates 7c,e. 8, 9 To explore the chemistry of compound L , we treated it with transition‐metal compounds such as [V(CO) 4 (Cp)], [Co(CO) 2 (Cp)], and Co 2 (CO) 8 .…”