Di-TERT-BUTYLMETHYL-SILANOL, -SILANOLATE UND -SILOXANE

Recent Developments in the Synthesis and Structure of Organosilanols

“…These are discussed below. The molecular structure of 1,3,5,7-tetrasiloxane-1,7-diol, Ph 2 (OH)Si(OSiPh 2 O) 2 Si(OH)Ph 2 (54), is shown in Figure 9. The notable features of the molecular structure of 54 is the linearity of the central Si-OSi bond angle and the absence of any intermolecular O-H‚‚‚O hydrogen bonding.…”

“…Monosilanols are the largest family of silanols. These are of three types: (a) R 3 SiOH [e.g., Me 3 SiOH, [26][27][28] Et 3 SiOH, 9,29,30 n-Bu 3 SiOH, 32,33 t-Bu 3 -SiOH, s-Bu 3 SiOH, 34 (c-C 6 H 11 ) 3 SiOH, 35,36 Ph 3 SiOH, 9,37,38 (1-naphthyl) 3 SiOH, 39 (t-BuO) 3 SiOH, 19,[40][41][42][43] (Me 3 SiO) 3 -SiOH, 44 (PhMe 2 SiO) 3 SiOH, 44 (neo-C 5 H 12 O) 3 SiOH 45 ]; (b) R 2 R′SiOH [e.g., Me 2 EtSiOH, 46 t-Bu 2 MeSiOH, 47 (n-C 6 H 11 )Me 2 SiOH, 46 (SiMe 3 ) 3 C(Me) 2 SiOH, 48,49 (SiMe 3 ) 3 -C(Et) 2 SiOH, 50 t-Bu 2 SiClOH, 51 t-Bu 2 SiBrOH, 51 t-Bu 2 -Si(NH 2 )OH, 52 (PhCHCl)Me 2 SiOH, 53 (PhCHBr)Me 2 -SiOH, 53 (t-Bu 2 MeSiO) 2 SiFOH, 47,54 (Me 3 SiO) 2 (PhMe 2 -SiO)SiOH, 44 (Me 3 SiO)(PhMe 2 SiO) 2 SiOH, 44 [MeO-(CH 2 ) 2 O(CH 2 ) 4 ]Me 2 SiOH, 46 (PhMe 2 Si) 3 CSiMe 2 OH, 46 [(Me 3 SiO)(Me 2 SiO)] 2 SiMeOH, 55 [(SiMe 3 ) 2 C(SiMe 2 Br)]-SiMe 2 OH, 56 (neo-C 5 H 11 O)Me 2 SiOH 57 ]; (c) RR′R′′SiOH [e.g., PhMe(1-naphthyl)SiOH, 58 (SiMe 3 ) 3 CSi(Ph)- (OMe)OH,…”

“…Although 66 is dimeric as a result of intermolecular P-OH interactions, the Si-OH units contained in this molecule do not participate in intermolecular hydrogen bonding. The molecular structure of 1,3,5,7-tetrasiloxane-1,7-diol, Ph 2 (OH)Si(OSiPh 2 O) 2 Si(OH)Ph 2 (54), is shown in Figure 9. The notable features of the molecular structure of 54 is the linearity of the central Si-O-Si bond angle and the absence of any intermolecular O-H‚‚‚O hydrogen bonding.…”

“…Monosilanols are the largest family of silanols. These are of three types: (a) R 3 SiOH [e.g., Me 3 SiOH, − Et 3 SiOH, ,, n -Bu 3 SiOH, , t -Bu 3 SiOH, s -Bu 3 SiOH, ( c -C 6 H 11 ) 3 SiOH, , Ph 3 SiOH, ,, (1-naphthyl) 3 SiOH, ( t -BuO) 3 SiOH, ,− (Me 3 SiO) 3 SiOH, (PhMe 2 SiO) 3 SiOH, ( neo -C 5 H 12 O) 3 SiOH]; (b) R 2 R‘SiOH [e.g., Me 2 EtSiOH, t -Bu 2 MeSiOH, ( n -C 6 H 11 )Me 2 SiOH, (SiMe 3 ) 3 C(Me) 2 SiOH, , (SiMe 3 ) 3 C(Et) 2 SiOH, t -Bu 2 SiClOH, t -Bu 2 SiBrOH, t -Bu 2 Si(NH 2 )OH, (PhCHCl)Me 2 SiOH, (PhCHBr)Me 2 SiOH, ( t -Bu 2 MeSiO) 2 SiFOH, , (Me 3 SiO) 2 (PhMe 2 SiO)SiOH, (Me 3 SiO)(PhMe 2 SiO) 2 SiOH, [MeO(CH 2 ) 2 O(CH 2 ) 4 ]Me 2 SiOH, (PhMe 2 Si) 3 CSiMe 2 OH, [(Me 3 SiO)(Me 2 SiO)] 2 SiMeOH, [(SiMe 3 ) 2 C(SiMe 2 Br)]SiMe 2 OH, ( neo -C 5 H 11 O)Me 2 SiOH]; (c) RR‘R‘ ‘SiOH [e.g., PhMe(1-naphthyl)SiOH, (SiMe 3 ) 3 CSi(Ph) (OMe)OH, (PhMe 2 Si) 3 CSi(Me)(H)OH, (Cp*(CO) 2 Fe)Si( p -tolyl)(H)OH, (Cp(CO) 2 Fe)Si( i -Pr)(H)OH, (Cp*(CO) 2 (PMe 3 )Fe)SiMe(H)OH 61 ] etc. Examination of all of these silanols reveals that the Si−OH group is reasonably robust and present in various types of compounds which contain many types of bonds such as Si−C, Si−H, Si−M, Si−O, Si−F, Si−Cl, Si−I or Si−Br.…”

The Course of (R2R‘SiO)3TaCl2 (R = tBu, R‘ = H, Me, Ph, tBu (silox); R = iPr, R‘ = tBu, iPr) Reduction Is Dependent on Siloxide Size

“…Recent crystal structures of t Bu 3 SiONa and t Bu 2 PhSiONaprepared via N 2 O treatment of the respective sodium silicidesreveal these species to be tetramers, with Na and O atoms occupying alternate corners of a cube . A related structure of t Bu 2 MeSiONa has also been determined 1 1 H NMR (δ ( J , Hz), assignt) 13 C{ 1 H} NMR (δ, assignt) compound t BuR/R‘/otherSiCMe 3 , SiC( C H 3 ) 3 R/R‘/other t Bu 2 MeSiH b 0.99 −0.01 (d, 4), Me t Bu 2 PhSiH c 1.02 3.63 (q, 4), SiH i Pr 2 t BuSiH d 1.02 1.11 (d, 7.5), Me 1.13 (d, 7.5), Me 3.54, SiH t Bu 2 MeSiOH e 0.97 −0.03, Me t Bu 2 PhSiOH 1.02 7.21 (dd, 2, 5), p -Ph 21.14, 30.09 128.31, Ph 7.44 (dd, 2, 8.5), m -Ph 133.94, Ph 7.64 (m, 2), o -Ph 144.28, Ph i Pr 2 t BuSiOH d 0.99 1.07 (d, 5.6) i Pr 3 SiOH d 1.03 (d, 7.5), Me 12.15, CH 3.59 (q, 2), OH 18.28, Me t Bu 2 HSiONa 1.03 4.37 (SiH) t Bu 2 MeSiONa 1.02 −0.06, Me t Bu 2 PhSiONa 1.11 7.11 (m, 4.8), m -Ph 7.71 (dd, 1.6), o , p- Ph i Pr 2 t BuSiONa 1.06 1.14 (d, 7), Me 1.15 (d, 7), Me i Pr 3 SiONa 1.08 (d, 7), Me 0.91 (sep, 7), CH ( t Bu 2 HSiO) 3 TaCl 2 ( 1 -H) ( t Bu 2 MeSiO) 3 TaCl 2 ( 1 -Me) 1.15 0.31, Me 21.54, 27.86 −7.07, Me ( t Bu 2 PhSiO) 3 TaCl 2 ( 1 -Ph) 1.31 7.19 (m, 2, 8), m -Ph …”