A systematic investigation has been made into the degree of silylium ion character in species of the type i-Pr 3 SiY where Yis a weakly coordinating hexahalo-carborane anion, X 6 -CB 11 H 6 -, with X ) Cl, Br, I. By X-ray crystal structural criteria such as the average C-Si-C angle (117.3(4)°, 117.0(13)°, and 115.6(9)°for X ) Cl, Br, I, respectively) and the downfield 29 Si chemical shift (115, 110, and 97 ppm for X ) Cl, Br, I, respectively) the hexachloro-carborane anion is the least coordinating. Thus, the "ion-like" species i-Pr 3 Si δ+ (Cl 6 -CB 11 H 6 ) δbecomes the closest structural approach to date to a condensed phase silylium ion. With the aid of ab initio molecular orbital theory and silicon chemical shift calculations we address the question of how much silylium ion character this species represents. From structural, energetic, and NMR criteria (where expectation values for the condensed phase 29 Si chemical shifts are revised downward) we conclude that i-Pr 3 Si δ+ (Cl 6 -CB 11 H 6 ) δmay have >50% silylium ion character.

The crystal structure of the tri-isopropyl silyl species, i-Pr(3)Si(Br(6)-CB(11)H(6)), where the brominated carborane Br(6)-CB(11) H(6)(-) is perhaps the least nucleophilic anion presently known, has revealed the highest degree of silylium cation character (R(3)Si(+)) yet observed. The average C-Si-C angle is 117 degrees , only 3 degrees short of the planarity expected of a pure silylium ion(120 degrees ). This value compares to 114 degrees recently reported for a toluene-solvated silyl cation, [Et(3)Si(toluene)](+) by Lambert and co-workers. The greater silylium ion character of i-Pr(3)Si(Br(6)-CB(11)H(6)) versus [i-Pr(3)Si(toluene)](+) is also reflected in the larger downfield shift of the silicon-29 nuclear magnetic resonance, 109.8 versus

Our previous studies of the captioned transition have shown that thermally sensitive poly(Nisopropylacrylamide) (PNIPAM) in water can form stable individual single-chain globules, but not for polystyrene (PS) in cyclohexane. In the current study, using poly(N,N-diethylacrylamide) (PDEAM) (M w ) 1.7 × 10 7 g/mol and M w /M n ) 1.06) with no hydrogen donator site, we intend to find whether the intrachain hydrogen bonding plays a role in stabilizing individual collapsed PNIPAM single-chain globules. We found that PDEAM can also form stable single-chain globules in water even though the transition is less sharp. The resultant individual PDEAM single-chain globules are less compact, reflecting in a lower chain density and a higher ratio of the radius of gyration to hydrodynamic radius, presumably due to the lack of intrachain hydrogen bonding. Our result also shows that, unlike PNIPAM, there is no hysteresis in the transition, indirectly supporting our previous assumption that the hysteresis observed for PNIPAM is due to the formation of some intrachain additional hydrogen bonds formed in the collapsed state.