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.
The synthesis and single crystal X-ray structures of the cobalt(II) complexes Co{N(SPPh
2)
2}
2
1, Co{N(SPPr
2
i)
2}
2
2, Co{N(SePPh
2)
2}
2
3 and Co{N(SePPr
2
i)
2}
2
4, synthesised by the reaction ...of cobalt(II) acetate with the sodium salt of the appropriate ligand in methanol are reported. All four compounds consist of discrete, monomeric molecules in which the ligands are found to be bidentate, conferring a distorted tetrahedral co-ordination geometry around the cobalt centres. The resulting MX
2P
2N rings are found to be puckered. The
31P NMR studies of compounds
1–
3 reveal one peak for each complex shifted upfield of the standard, whereas that for
4 is found downfield. The synthesis of NH(SePPr
2
i)
2}
2 is reported for the first time.
We report the synthesis and structural characterisation of three five co-ordinate indium(III) bis-chelate complexes of imidodiphosphinates with general formula InCl{N(PR
2X)
2}
2, (R=Ph or Pr
i, X=S ...or Se), formed from the 1:2 reaction of indium(III) trichloride and the potassium or sodium salt of the ligand in methanol/THF. The complexes consist of discrete monomeric, molecules and show a trigonal–bipyramidal co-ordination pattern. These are the first examples of five co-ordinate complexes containing this type of ligand, in contrast to other indium(III) and main group element complexes of similar ligands in which only the six co-ordinate tris-chelates are known.
Polymorphism in ammonium 2,4,6-trimethylbenzenesulfonate AUCOTT, Stephen M; DALE, Sophie H; ELSEGOOD, Mark R. J ...
Acta crystallographica. Section C, Crystal structure communications,
03/2005, Letnik:
61, Številka:
Pt 3
Journal Article
Recenzirano
Odprti dostop
During investigations into sulfide- and selenide-amination reactions using the aminating agent o-mesitylsulfonylhydroxylamine, the monoclinic, (I), and orthorhombic, (II), polymorphs of ammonium ...2,4,6-trimethylbenzenesulfonate, NH4+.C9H11O3S-, have been crystallized. Investigation of the hydrogen-bonding motifs within the two polymorphs shows that both contain N+-H...O- hydrogen bonds between the ammonium cations and the 2,4,6-trimethylbenzenesulfonate anions. Polymorph (I) contains R(4)(4)(12) and R(4)(2)(8) graph-set ring motifs, while polymorph (II) contains the same R(4)(4)(12) ring motif in combination with an R(4)(3)(10) motif. The two hydrogen-bonding patterns result in slightly different packing structures for the two polymorphs, but both are based on a thick-sheet arrangement, in which the NH4+ cations are enveloped between two layers of 2,4,6-trimethylbenzenesulfonate anions. In (I), the aromatic rings of the anions are approximately coplanar, giving parallel sheets, whereas in (II) the sheets are antiparallel and the anions pack in a herring-bone manner within the sheets, with angles of 78.76 (8) degrees between the planes of the aromatic rings.
N-(Diphenylselenio)diphenylsulfimidium tetraphenylborate Aucott, Stephen M; Dale, Sophie H; Elsegood, Mark R J ...
Acta crystallographica. Section C, Crystal structure communications,
02/2005, Letnik:
61, Številka:
Pt 2
Journal Article
Recenzirano
Odprti dostop
The title compound, C24H20NSSe+.C24H20B-, exhibits disorder (S/Se scrambling) of the chalcogen sites within the S-N-Se triad. Similar disorder was observed in the bromide salt Aucott, Bailey, ...Elsegood, Gilby, Holmes, Kelly, Papageorgiou & Pedron-Haba (2004). New J. Chem. pp. 959-966. The S-N and Se-N bond lengths are 1.6735 (15) and 1.8045 (14) A, respectively. Whereas the chalcogens in the bromide salt are involved in S...Br and Se...Br interactions of very similar distances, the scrambled S and Se sites in the title compound are involved in distinct non-bonded interactions. The site predominantly occupied by sulfur is involved in C-H...S/Se interactions, while the site predominantly occupied by selenium is involved in Se/S...pi interactions.
The title compound, (C30H25NPS)2Pd2Br6 or (Ph3PNSPh2)2Pd2Br6, was crystallized from the reaction of (Ph3PNSPh2)BPh4 with (PPh4)2Pd2Br6, giving a salt rather than the intended coordination complex ...PdBr3(Ph3PNSPh2). The compound crystallizes in the non‐centrosymmetric space group Cc with one complete formula unit in the asymmetric unit. One of the two independent cations is disordered. The geometry of the two cations is compared with that of the only previously crystallized example of this cation, viz. its SbCl6− salt Reck et al. (1982). Chem. Ber. 115, 2981–2996. The bond angles within the P—N—S triad in the two cations in the title compound are narrower than those observed in the literature example, while the S—N bond lengths are slightly longer in the title compound. The P—N bond length in the ordered cation shows excellent agreement with that determined by Reck and co‐workers, but the P—N bond lengths are lengthened slightly in the disordered cation. Weak C—H·Br interactions create a three‐dimensional network, with cations and anions alternating along the crystallographic c direction.
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