The preparation and properties of α-tin ketones

Silicon-transition metal chemistry. 9. Synthesis, properties, and structure of the rhenium acylsilane complex fac-Re(CO)3(diphos)[C(O)SiPh3]

“…Experimental Section Starting Materials. Trimethylphosphine was prepared according to the method of Markham et al 13 from the reaction of MeLi (Alfa Inorganics, Beverly, Mass.,) with PC13 (Anachemia, Toronto) in an ethereal solution. The product was checked for purity by vapor pressure measurement (160 mm at 0 °C; lit.…”

“…We reported recently the synthesis of /ac-Re(CO)3(diphos)[C(0)SiPh3] (1) by this route and noted its remarkable spectroscopic properties. 7 The cation [Re-(CO)4(diphos)]+ had been chosen for this work because (i) known to undergo attack by nucleophiles at carbonyl carbon atoms,8,9 (iii) the resulting trisubstituted octahedral complex, particularly with facial stereochemistry, would be expected to have relatively nonlabile CO ligands,10 thereby inhibiting a decarbonylation pathway promoted by dissociation of CO cis to the acyl ligand,11 and (iv) the steric bulk of the diphos ligand could provide stability to the resultant acyl complex by hindering subsequent attack of R3M/Li at the acyl carbon atom.12, 13 We now report the structure of 1 as determined by x-ray crystallography and discuss more fully its physical and chemical properties.…”

Organogermanium(iv) compounds in photo-induced radical reactions

“…Among these structures, only acylgermanes have absorption in the visible spectrum and can undergo cleavage after being directly excited; whereas the others require UV irradiation for direct photolysis (Scheme 1a). [53][54][55][56][57][58] As for SET oxidation, according to the literature, all of these compounds have oxidation potentials suitable for visible-light photocatalysis, indicating their activities too (Scheme 1b). 20,21,[59][60][61] In this review, we summarize the applications and reaction mechanisms of these four classes of organogermanium compounds in photoinduced radical reactions, respectively.…”

“…After which, the methyl radical would react with another trimethylgermane molecular via a HAT process to give the relatively stable trimethylgermyl radical. 94 Meanwhile, triphenylgermane (54) prefers to generate a triphenylgermyl radical and hydrogen radical via direct homolysis under irradiation (Scheme 8a). 56 When using alkenes as radical acceptors, the radical addition process could lead to the alkyl radical 55, which would undergo a secondary HAT process with another trimethylgermane to yield 56 and complete the radical propagation process (Scheme 8b).…”