Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes PtCl4(RCN)2 ...proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds PtCl4{NHC(R)NSR‘Ph}2 (R‘ = Ph, R = Me, Et, CH2Ph, Ph; R‘ = o- and p-(PhS)C6H4; R = Et). While trans-PtCl4(RCN)2 (R = Et, CH2Ph, Ph) reacting with Ph2SNH leads exclusively to trans-PtCl4{NHC(R)NSPh2}2, cis/trans-PtCl4(MeCN)2 leads to cis/trans mixtures of PtCl4{NHC(Me)NSPh2}2 and the latter have been separated by column chromatography. Theoretical calculations at both HF//HF and MP2//HF levels for the cis and trans isomers of PtCl4{NHC(Me)NSMe2}2 indicate a higher stability for the latter. Compounds trans-PtCl4{E-NHC(R)NSPh2}2 (R = Me, Et) and cis-PtCl4{E-NHC(Me)NSPh2}{Z-NHC(Me)NSPh2} have been characterized by X-ray crystallography. The complexes PtCl4{NHC(R)NSPh2}2 undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines PtCl4{NHC(NH2)R}2 (the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes PtCl4{NHC(R)NSR‘Ph}2 by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NHC(R)SR‘Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-{PhS(NH)}(PhS)C6H4 also react with the Pt(II) nitrile complex PtCl2(MeCN)2 but the couplingin contrast to the Pt(IV) speciesgives the chelates PtCl2{NHC(Me)NS(Ph)C6H4SPh}. The X-ray crystal structure of PtCl2{NHC(Me)NS(Ph)C6H4SPh-o} reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.
Treatment of 1,4-(PhS)2C6H4 and 1,2-(PhS)2C6H4 with the appropriate amount of O-mesitylenesulfonylhydroxylamine (MSH) yields the corresponding protonated sulfimides, both of which may be deprotonated ...with 1,8-diazabicyclo5.4.0undec-7-ene (DBU) to give the hydrated free sulfimides 1,4-(PhS{NH2})2C6H4 and 1,2-(PhS{NH2})C6H4PhS. It would seem that both products display the ability to give two distinct types of material, anhydrous and hydrated forms. The hydrated type 1,4-(PhS{NH2})2C6H4.2H2O has been found by crystallography to form an extended array system; whereas the crystal structure of the dehydrate exhibits extra structural "rigidity" brought about by having two hydrogen-bonded sulfimide units per molecule. The ligand 1,2-(PhS{NH2})C6H4PhS also exhibits two distinct types of formation, one a dehydrate (exhibited as an oil) and the other a hydrated type (present as a crystalline solid).
Treatment of 1,4-(PhS)2C6H4 and 1,2-(PhS)2C6H4 with the appropriate amount of O-mesitylenesulfonylhydroxylamine (MSH) yields the corresponding protonated sulfimides, both of which may be deprotonated ...with 1,8-diazabicyclo5.4.0undec-7-ene (DBU) to give the hydrated free sulfimides 1,4-(PhS{NH2})2C6H4 and 1,2-(PhS{NH2})C6H4PhS. It would seem that both products display the ability to give two distinct types of material, anhydrous and hydrated forms. The hydrated type 1,4-(PhS{NH2})2C6H4.2H2O has been found by crystallography to form an extended array system; whereas the crystal structure of the dehydrate exhibits extra structural "rigidity" brought about by having two hydrogen-bonded sulfimide units per molecule. The ligand 1,2-(PhS{NH2})C6H4PhS also exhibits two distinct types of formation, one a dehydrate (exhibited as an oil) and the other a hydrated type (present as a crystalline solid).
Treatment of 1,4-(PhS)2C6H4 and 1,2-(PhS)2C6H4 with the appropriate amount of O-mesitylenesulfonylhydroxylamine (MSH) yields the corresponding protonated sulfimides, both of which may be deprotonated ...with 1,8-diazabicyclo5.4.0undec-7-ene (DBU) to give the hydrated free sulfimides 1,4-(PhS{NH2})2C6H4 and 1,2-(PhS{NH2})C6H4PhS. It would seem that both products display the ability to give two distinct types of material, anhydrous and hydrated forms. The hydrated type 1,4-(PhS{NH2})2C6H4.2H2O has been found by crystallography to form an extended array system; whereas the crystal structure of the dehydrate exhibits extra structural "rigidity" brought about by having two hydrogen-bonded sulfimide units per molecule. The ligand 1,2-(PhS{NH2})C6H4PhS also exhibits two distinct types of formation, one a dehydrate (exhibited as an oil) and the other a hydrated type (present as a crystalline solid).
This article reports on the effectiveness of an early intervention program,
'Adolescents Coping with Emotions' (ACE), for depression in girls. ACE
was assessed in a short-term wait-list control ...trial. In 1999, 882 students
(aged 13-16 years) were screened using the Children's Depression Inventory
(CDI). One hundred and seventy-nine students (63% female) who scored above the
CDI cutoff (of 18) were offered the program and 143 (65% female) agreed to
participate. On a school basis, participants were allocated to the intervention
group (
n
= 76; 56% female) who commenced the program within one month, or to a wait-list
control condition (control group,
n
= 50; 79% female) who commenced the ACE program after 10 weeks. Data analysis
was conducted for 82 female participants. All students completed the CDI,
Adolescent Coping Scale and Children's Automatic Thoughts Scale at pre-And
post-intervention. The intervention group also
completed a 6-month follow-up. At post-intervention, female ACE participants
reported significantly reduced depressive symptoms and significantly improved
coping skills compared with the control group. Using cognitive-behavioural and
interpersonal techniques, the ACE program diminished depressive symptoms and
increased coping skills in girls screening at-risk for depression.
