Mechanistic studies on the alcoholysis and aminolysis of [(MeZn)2{μ-N(H)tBu}{μ-N(CH2Py)2}]

Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

“…28) was synthesized serendipitously by the reaction between Sr(OR) 2 [R = dibenzylphenyl] and silicon lubricant (Me 2 SiO) n [122]. This is not surprising because similar reactions between dimethylpolysiloxane (also a silicone lubricant) with organic derivatives of alkali metals [123], polyvalent metal halides [124], and organic derivatives of main group metals [125] yield previously reported metallasiloxanes, e.g., compound 83 was obtained using this method [120]. It is notable that despite the simplicity of splitting polysiloxane using organometallic derivatives, this method is not used widely to prepare PHMSs because the results are often difficult to predict.…”

“…PHMSs bearing few polyvalent metal atoms (e.g. 83 [120]) or mixed-metal PHMSs such as 84, [121] can be formed from only one or two disiloxane fragments (Fig. 27).…”

Serendipitous reactions involving a silicone grease

“…In the course of the study on the reactivity of zinc methoxides, (MeZn) 2 (-OMe)[-N(CH 2 Py) 2 ] 38 was treated with t-butylamine and the resulting solution was stored at 5 • C for 2 weeks to afford colorless crystals of trinuclear zinc complex 39 having an Si O Si unit, which was accidentally introduced from a silicone grease present in a sealed ground glass joint (Scheme 11) [33]. Scheme 11.…”

Zinc, cadmium and mercury

“…A related study of the alcoholysis and aminolysis of a zincmethyl compounds has been reported. 7 It is interesting to note different behaviour of the bis(phosphinimino)methanide ligand at zinc, depending on the chemistry under investigation. For example, [CH 2 {Ph 2 PQNSiMe 3 } 2 ] (L-H) forms simple adducts [(L-H)ZnCl 2 ] and [(L-H)ZnI 2 ], but is deprotonated at the methylene group when reacted with ZnPh 2 to afford [(L)ZnPh].…”

“…In the context of the former area, previous research has suggested that the toxic effects of mercury may be derived from its influence on the biochemistry of selenium. Understanding the chemistry of the Hg-Se bond was therefore probed in a study using compounds supported by the tris(2-mercapto-1-t-butyl-imidazolyl)hydroborato ligand (7), concluding that the apparent covalent radius of the metal is not only molecule dependent, but also bond dependent. 51 Other ligands that bind via selenium include the simple pentafluorophenyl selenolate, [C 6 F 5 Se] À , accessed by reductive cleavage of the diseleno-precursor, [(C 6 F 5 )Se-Se(C 6 F 5 )].…”