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Extremely bulky secondary phosphinoamines as substituents for sterically hindered aminosilanes

“…In ether solutions it readily decomposes to yield 5 as the only product containing a phosphorus atom. 21 For compound 9, the elimination process is apparently triggered by Lewis bases (Scheme 5). N.B.…”

“…The N1-P1 and N1-Si1 bond lengths increase on going from 5 to 8. 21 To explore the chemistry of more silicon rich chloro-aminosilanes, addition of one equivalent 1-Li to a solution of the cyclic chlorosilane Si 5 Cl 10 in toluene was carried out, and this afforded 11. The 31 P NMR spectroscopic signal for 8 (δ 59.6 ppm) is shifted slightly upfield compared with that for 5 (δ 65.7 ppm), which is in accord with the positions of the 29 Si NMR spectroscopic signals for 5 (δ −29.4 ppm) and 8 (δ -47.1 ppm, 1 J SiH = 218 Hz).…”

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…The same research group synthesized [143,144] other transition metal derivatives to study its reactivity with LiAlH 4 and the corresponding pentahydridodisilane product from dimethyldioxirane treatment. These investigations were motivated by a desire to understand the electronic effect of various transition metal centers on the reactivity of the ␣-and ␤-silicon in disilanyl complexes.…”

Reinvestigation of the Pd-catalyzed bis(silylation) of alkynes with 1,1,2,2-tetramethyl-1,2-bis(phenylthiomethyl)disilane: Unexpected formation of the eight-membered siloxane–chelate complex cis-[PdCl2{(PhSCH2SiMe2)2O}]

“…The crystal structure is presented in Fig. 1, the crystal and refinement data are listed in Table 1. In the centrosymmetric molecule, the SieSi bond distance is somewhat shorter than in fac-[{RuCl 2 (CO) 3 3,4,4,8,8,9,9-octamethyl-1,6-dithia-3,4,8,9-tetrasilacyclodecane (2.3450(4) A) [29]. There are neither intermolecular nor intramolecular interactions between the sulphur atoms and the silicon centres.…”

“…For example, HR 2 SieSiR 2 H (R ¼ Me, Ph) have been used in oxidative addition reactions across [(MeCp)Mn(CO) 2 (THF)], [CpRe(CO) 2 (THF)] and [Fe(CO) 4 PPh 3 ] for the synthesis of hydrido disilanyl complexes [1]. Disilanyl complexes [CpM(CO) 3 3 ] has led to the bis(silyl) complex cis-[Pt(HMe 2 Si) 2 (PEt 3 ) 2 ] [5]. Even the unactivated disilane hexamethyldisilane can be oxidatively added across [Pt(PEt 3 ) 3 ] to provide cis-[Pt(Me 3 Si) 2 (PEt 3 ) 2 ] [6].…”