Matrix Reactivity of Zn, Cd, or Hg Atoms (M) in the Presence of Silane:  Photogeneration and Characterization of the Insertion Product HMSiH₃in a Solid Argon Matrix

Abstract

Matrix-isolation experiments give evidence that broad-band UV-vis irradiation (200 e λ e 800 nm) of an Ar matrix doped with SiH 4 and a group 12 metal atom M (M ) Zn, Cd, or Hg) induces metal insertion into an Si-H bond to give the silyl metal hydride molecule HMSiH 3 as the primary product. Si 2 H 6 is a second product, irrespective of the identity of M, while the binary hydride MH 2 is also formed when M ) Zn or Cd. The products have been identified by their IR spectra and experiments with SiD 4 , together with the results of quantum chemical calculations, have provided the means of authentication. The properties of the HMSiH 3 molecules are compared with those of related species, and consideration is given to how the products come to be formed.

Matrix Reactivity of Al and Ga Atoms (M) in the Presence of Silane: Generation and Characterization of the η2‐Coordinated Complex M⋅SiH4, the Insertion Product HMSiH3, and the MISpecies MSiH3in a Solid Argon Matrix

“…Disilane, Si 2 H 6 , is a known secondary product of similar matrix reactions involving a Group 12 metal atom such as Zn. [6,39] The possibility that this or the SiH 3 C radical is being formed by the present reactions can be largely discounted by comparison with the spectra recorded previously for these species under matrix conditions. [6,40] The precedents of earlier matrix studies are that divalent aluminum or gallium hydrides, such as HMOH, [29] HMNH 2 , [24] HMCH 3 , [15,16] and HMH, [25] are photolabile and decompose under the action of broadband UVvisible irradiation through cleavage of the M À H bond to form the appropriate M I compound and HC atoms.…”

Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

“…Baumgartner and co-workers reported reactions of oligosilylalkynes with Co 2 (CO) 8 in which Si-Si bond activation appears to occur in the coordination sphere of the cobalt atoms. 233 An example is required photolysis to give the Si-C cleavage product (dcpe)Pt(SiMe 3 )(CtCPh) (19)(20)(21)(22)(23)(24)(25). 423 One of the more novel transformations involved reaction of the bis (COD)Pt adduct of 1,4-bis(trimethylsilyl)-1,3-butadiyne with PN, which then gave the bisplatinum complex (PN)Pt(SiMe 3 )CtC-CtCPt-(SiMe 3 )(PN) (19)(20)(21)(22)(23)(24)(25)(26).…”

Consecutive fragmentations of the cubane-like zinc cluster [CH3Zn(O-i-C3H7)]4upon electron ionization

“…Formation of HZnOi-C 3 H 7 is assumed by analogy to the insertion species HZnOH whose existence has been demonstrated by matrix-isolation spectroscopy. 36,37 Once more, however, the neutral fragment(s) might also correspond to the products of reductive elimination, i.e. Zn þ i-C 3 H 7 OH.…”