Reactions of PH(3) and commercially available H(2)C=CHR(f) (R(f6)(/)(8)(/)(10) = (CF(2))(5)CF(3)/(CF(2))(7)CF(3)/(CF(2))(9)CF(3)) give, in two-stage processes conducted with free radical initiators (AIBN, VAZO; 80-90 degrees C), the phosphines P(CH(2)CH(2)R(f))(3) (1-3; 63-75%). Analogous reactions with H(2)C=CHCH(2)R(f8) (7) and H(2)C=CHCH(2)CH(2)R(f8) (10) give P(CH(2)CH(2)CH(2)R(f8))(3) (4, 73%) and P(CH(2)CH(2)CH(2)CH(2)R(f8))(3) (5, 66%), in which the phosphorus is increasingly insulated from the electronegative R(f) moiety. The alkenes 7 and 10 are prepared from Bu(3)SnCH(2)CH=CH(2) and IR(f8) (hnu, CH(2)Cl(2), 81%) or ICH(2)R(f8) (VAZO, refluxing CF(3)C(6)H(5), 56%). The reaction of 1 and H(2)O(2) gives O=P(CH(2)CH(2)R(f6))(3) (6, 88%), which can be reduced with HSiCl(3) to 1. Partition coefficients (CF(3)C(6)F(11)/toluene, 27 degrees C) range from 98.8:1.2 (1, 4) through 98.9:1.1 (5) to >99.7:<0.3 (2, 3, 6). Crystals of 4 diffract poorly, but a packing motif that maximizes interactions between R(f) segments is evident.

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The present work entails the synthesis and first structural characterization of complexes possessing a single Al−O−Si linkage. These are of the formula LAlOSiPh3 (L = Salen(tBu) (N,N‘-ethylenebis(3, 5-di-tert-butylsalicylideneimine)) (11); Salpen(tBu) N,N‘-propylenebis(3,5-di-tert-butylsalicylideneimine)) (12); Salophen(tBu) (N,N‘-phenylenebis(3,5-di-tert-butylsalicylideneimine)) (13); and Salomphen(tBu) (N,N‘-(3,4-dimethylphenylene)bis(3,5-di-tert-butylsalicylideneimine)) (14). They are formed by combining the novel five-coordinate aluminum alkyl starting materials L(tBu)AlR (where L = Salen(tBu), R = Me (1), Et (2), iBu (3); Salpen(tBu), R = Me (4), Salophen(tBu) R = Me (5), Et (6), iBu (7); and Salomphen, R = Me (8), Et (9), iBu (10)) with Ph3SiOH in toluene. All of the compounds were characterized spectroscopically and, in the case of 1, 10, 11, 12, and 13, by X-ray crystallography.

Herein are described the synthesis and characterization of the complexes of formula LAlR (where R = Cl and L = Salen (1), SalenCl (2), Acen (3) and where R = Me and L = Salen (4), SalenCl (5), Acen (6); Salen = N,N'-ethylenebis((2-hydroxyphenyl)methylimine), SalenCl = N,N'-ethylenebis((2-hydroxy-5-chlorophenyl)methylimine), Acen = N,N'-ethylenebis((2-hydroxyphenyl)-1-ethylimine)). The LAlCl derivatives dissolve in water and MeOH to yield the cationic complexes [LAl(H(2)O)(2)](+)Cl(-) (L = Salen (7), SalenCl (8), Acen (9)) and [LAl(MeOH)(2)](+)Cl(-) (L = Salen (10), SalenCl (11), Acen (12)), respectively. An alternative preparation of the cationic species involves the reaction of the LAlCl derivative with NaBPh(4). This leads to complexes of formula [LAl(MeOH)(2)](+)BPh(4)(-) (L = Salen (13), SalenCl (14), Acen (15)). Complexes 4-6 can be reacted with either MeOH or 4-chloro-3,5-dimethylphenol (Ph') to form complexes of general formula LAlOR (R = Me, L = Salen (16), SalenCl (17), Acen (18); R = Ph', L = Salen (19), SalenCl (20), Acen (21)). All of the compounds were characterized by IR, melting points, elemental analyses, and, when soluble, NMR. Additionally, the crystal structures of 7, 13, 15, and 18 were obtained.

Background Personal construct Theory (PCP) may provide a way for people who are violent and have schizophrenia to understand and modify their behaviour. The ability to reconstrue personal relationships may lead to greater acceptance of perceived or real stresses and increased tolerance. Method A year‐long pilot study tested the feasibility of PCP‐oriented psychotherapy amongst long‐term male residents with schizophrenia in Broadmoor Hospital, all of whom had committed violent acts. A matched group completed the same instruments, but did not receive group psychotherapy. Six of the eight subjects from the index group completed the therapy, but instrument compliance varied. Results for group data cannot be presented, but an individual case report is offered, demonstrating the changes in construing that occurred over the year. These included elaboration accompanied by changes in mood, and the formation of a more appropriate construct system for managing personal relationships. Conclusions The model for therapy is feasible within a secure environment, although there are ethical issues. The evaluation of outcome requires substantial modification, and the issue of subject cooperation needs further attention. The pilot does, however, suggest that such work is then worth more substantial study, including randomization between treatment and non‐treatment groups. Copyright © 1998 Whurr Publishers Ltd.

In the present manuscript we will detail the first use of the Salen(tBu)H2 ligands with the group 13 elements. This includes the compounds of formula Salen(tBu)AlCl (where Salen = Salen(N,N‘-ethylenebis(3,5-di-tert-butylsalicylideneimine)) (1), Salpen (N,N‘-propylenebis(3,5-di-tert-butylsalicylideneimine)) (2), Salophen (N,N‘-benzenylidenebis(3,5-di-tert-butylsalicylideneamine)) (3), and Salomphen (N,N‘-(3,4-dimethylbenzenylidene)bis(3,5-di-tert-butylsalicylideneimine)) (4)) and the novel five-coordinate monomeric amides of formula LAlNRR‘ (where L = Acen (N,N‘-ethylenebis((tBu)salicylidene(methyl)imine); R, R‘ = H, Ph (5); R = R‘ = SiMe3 (6)) and L = Salen (R, R‘ = H, tBu (7), H, Ph (8), and H, Dipp (2,6-diisopropylphenyl) (9); R = R‘ = Me (10), Et (11), and SiMe3 (12))). Additionally the unique monomeric hydroxy complex Salen(tBu)AlOH (13) and its condensation product, (Salen(tBu)Al)2O (14), will be described. All of the compounds were characterized by spectroscopic (1H, 13C, and 27Al NMR, IR) and physical (mp, analyses) techniques. X-ray crystallographic data are presented for 14.

Addition of a yellow-orange toluene solution of [Rh(Cl)(COD)]2 to a colorless CF3C6F11 solution of P(CH2CH2R f6 )3 (R f6 = (CF2)5CF3)3) gives a colorless toluene solution of COD and an orange CF3C6F11 solution of ClRh[P(CH2CH2R f6 )3]3 (1). Evaporation of CF3C6F11 gives analytically pure 1 (94%), which is insoluble in most organic solvents and stable to 300 °C. Alkenes, catecholborane, and CF3C6F11 solutions of 1 (950:950:1 mol ratio for norbornene) are stirred for 1−24 h at 40 °C (heterogeneous conditions). The resulting alkylboranes are extracted with benzene (2×; turnover number (TON) 854 (90%) for norbornene), toluene, or THF, and the catalyst solution is reused (TON 2409 for three cycles). Subsequent reactions with H2O2/NaOH give alcohols, which are isolated in 92−77% yields (11 examples). Longer reaction times afford TON values higher than 10 000 (<0.1 mol % 1). Analogous reactions of alkynes yield alkenylboranes (89−88%). Pinacolborane additions are also catalyzed. A higher homologue of 1, ClRh[P(CH2CH2R f8 )3]3 (2), and the nonfluorinated analogue ClRh[P((CH2)7CH3)3]3 are similarly prepared. Solubilities and reactivities are compared. Atomic absorption analyses shows rhodium losses of 0.4% (1) and 0.2% (2) per cycle, corresponding to 4.5−2.2 ppm rhodium/mol of addition product. These data demonstrate the viability and practicality of an exciting new approach to catalyst immobilization.

The absorption, disposition, metabolism and excretion study of orally administered 2,2',4,4',6-pentabromodiphenyl ether (BDE-100) was studied in conventional and bile-duct cannulated male rats. In conventional rats, >70% of the radiolabelled oral dose was retained at 72 h, and lipophilic tissues were the preferred sites for disposition, i.e. adipose tissue, gastrointestinal tract, skin, liver and lungs. Urinary excretion of BDE-100 was very low (0.1% of the dose). Biliary excretion of BDE-100 was slightly greater than that observed in urine, i.e. 1.7% at 72 h, and glucuronidation of phenolic metabolites was suggested. Thiol metabolites were not observed in the bile as had been reported in other PBDE metabolism studies. Almost 20% of the dose in conventional male rats and over 26% in bile-duct cannulated rats was excreted in the faeces, mainly as the unmetabolized parent, although large amounts of non-extractable radiolabel were also observed. Extractable metabolites in faeces were characterized by mass spectrometry. Monohydroxylated pentabromodiphenyl ether metabolites were detected; mono- and di-hydroxylated metabolites with accompanying oxidative debromination were also observed as faecal metabolites. Tissue residues of [(14)C]BDE-100 in liver, gastrointestinal tract and adipose tissue contained only parent material. The majority of the 0-72-h biliary radioactivity was associated with an unidentified 79-kDa protein or to albumin.