Synthesis, Structure, and Properties of {(Me₃Si)₂CH}₂SnH(OH)

Abstract

The Lappert stannylene SnR2, R = CH(SiMe3)2, adds water and methanol to yield the low-melting-point, crystalline hydroxy- and methoxydiorganostannanes R2SnH(OH) (1) and R2SnH(OMe) (2). The corresponding deuterated derivatives R2SnD(OD) (1-d 2) and R2SnD(OCD3) (2-d 4) have also been prepared. Compounds 1 and 2 react with D2O with retention of the Sn−H bond to give R2SnH(OD) (1-d(SnOD)). The reaction is thought to proceed by an SN2 type mechanism via a [R2SnH(OR‘)2]- (R‘ = H, D, or Me) intermediate or transition state. Consistent with this, 2-d 4 is hydrolyzed to R2SnD(OH) (1-d(SnD)). A single-crystal X-ray structure analysis of 1 reveals that individual molecules form C i -symmetrical dimers in the solid with short O−H···O* hydrogen bridges (O···O* = 2.854(2) Å). Reaction of 1 with (iPr2PC2H4PiPr2)Pd(C2H4) results in oxidative addition of the Sn−H bond to Pd0 to give the known (iPr2PC2H4PiPr2)Pd(H)−SnR2(OH) (3).

E–H Bond Activation of Ammonia and Water by a Geometrically Constrained Phosphorus(III) Compound

“…Interestingly,when the reaction is carried out at 70 8 8C, exchange of the phosphorus-bound hydride is also observed, providing a1:1 isotopic distribution. Therelative ease of H/D exchange is in agreement with aprevious report by Pçrschke et al [35] In addition to the previously observed doublet, attributable to the phosphorus center of 3,t he 31 PNMR spectrum of the reaction mixture also shows at riplet at d = À37.7 ppm ( 1 J P-D = 133 Hz). Acomplementary doublet is also Figure 3.…”

“…[23] Theo xidative activation of water is of immense current interest, representing ac rucial step in metal-catalyzed water splitting.D espite this fact, there are few transition-metal complexes that are able to effect this transformation. [2] Although there are several reports outlining similar reactivity at main group centers, [33][34][35][36][37][38][39][40][41] there are currently only two examples that are able to do so without the use of forcing conditions,n on-equimolar loadings of water, or secondary activating substrates. [37,41] Ther oom-temperature reaction of 3 with one equivalent of deuterium oxide results in exchange of the hydroxyl proton.…”

Hydroxo Hydrido Complexes of Iron and Cobalt (Sn−Fe−Sn, Sn−Co−Sn): Probing Agostic Sn⋅⋅⋅H−M Interactions in Solution and in the Solid State

“…for several hours. This is substantiated by the fact that the hydroxo hydrido diorganostannane 13, [13] containing H 2 O in a ªpreactivatedº form, does not react with the monometallic organoiron compound 9 to give 12. However, chromatography on freshly dried Al 2 O 3 , containing virtually no water, leaves 10 unchanged, clearly indicating the high reactivity of the iron ± tin complex 10 towards nucleophilic attack by trace amounts of water.…”

“…The IR spectra (KBr) of 12 and 15 display n(SnÀOHÀSn) stretching vibrations at 3650 (12) and 3615 cm À1 (15). [13] The bands from the n(FeÀH) and n(CoÀH) stretching modes in 12 and 15 are unfortunately broad and thus ill-defined, making a reliable assignment impossible. These frequencies are in accord with the nSn À OH À Sn stretching frequencies of the Ni complex [(h 5 -Cp)Ni{(SiMe 3 ) 2 CH} 2 Sn(OH)Sn{CH(SiMe 3 ) 2 } 2 ] [11] (n(OH) 3621 cm À1 ) and the hydroxo organostannane complex 13 (n(OH) 3660 cm À1 ).…”

Radiochemical study of gas-phase reactions of diethylstannyl cations Et2SnT+ with oxygen-containing compounds: II. Reaction of diethylstannyl cations with butanol

“…There are no published data on diorganylstannanols; obviously, such compounds are very unstable. Only when bulky trimethylsilyl groups were attached to tin, the hydrolysis of the corresponding tin(II) compound gave bis[bis(trimethylsilyl)methyl]stannanol [(Me 3 Si) 2 CH] 2 · SnH(OH) [12]. Diethylstannanol Et 2 SnH(OH) necessary as reference cannot be obtained by analogous procedure; according to published data, diethyltin is an oligomer [(C 2 H 5 ) 2 Sn] n [13,14], and it fails to react.…”