A series of complexes, ranging from the small cluster 1/infinity[Ag(Ph2PS2)(dppe)](infinity) [dppe=1,2-bis(diphenylphosphino)ethane] to [Cu48S20(O(t)Bu)2(Ph2PS2)2(dppm-)4(dppm)4][dppm=1,2-bis(diphenylphosphino)methane] (the largest Cu cluster containing phosphinodithioato ligands), has been synthesised. The structural evidence presented here indicates that in these reactions initially small cyclic aggregates or one-dimensional coordination polymers are formed. The growth of these intermediates to larger aggregates can take up to several months and could proceed via cationic intermediates.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/b501360g | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Activation and functionalisation of carbon dioxide by bis-tris(pyrazolyl)borate-supported divalent samarium and trivalent lanthanide silylamide complexes.
Dalton Trans
July 2024
School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow, G12 8QQ, UK.
Synthesis and reactivity with carbon dioxide (CO) of divalent samarium in the bis-tris(pyrazolyl)borate ligand environment has been reported. In addition, CO activation and functionalisation by lanthanide silylamides in the bis-tris(pyrazolyl)borate ligand environment was demonstrated. Reduction of the Sm(III) precursor [Sm(Tp)(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with KC yielded the insoluble Sm(II) multi-metallic coordination polymer [{Sm(Tp)}] 1-Sm.
View Article and Find Full Text PDFModelling local structural and electronic consequences of proton and hydrogen-atom uptake in VO with polyoxovanadate clusters.
Chem Sci
October 2021
Department of Chemistry, University of Rochester Rochester NY 14627 USA
We report the synthesis and characterisation of a series of siloxide-functionalised polyoxovanadate-alkoxide (POV-alkoxide) clusters, [VO(OSiMe)(OMe)] ( = 1-, 2-), that serve as molecular models for proton and hydrogen-atom uptake in vanadium dioxide, respectively. Installation of a siloxide moiety on the surface of the Lindqvist core was accomplished addition of trimethylsilyl trifluoromethylsulfonate to the fully-oxygenated cluster [VO(OMe)]. Characterisation of [VO(OSiMe)(OMe)] by X-ray photoelectron spectroscopy reveals that the incorporation of the siloxide group does not result in charge separation within the hexavanadate assembly, an observation that contrasts directly with the behavior of clusters bearing substitutional dopants.
View Article and Find Full Text PDFBidentate Lewis Acids Derived from o-Diethynylbenzene with Group 13 and 14 Functions.
ChemistryOpen
October 2021
Chair of Inorganic and Structural Chemistry, Center of Molecular Materials CM2, Bielefeld University, Universitätsstraße 25, D-33615, Bielefeld, Germany.
Starting from 1,2-diethynylbenzene, a series of bidentate Lewis acids was prepared by means of hydrometalations, in particular hydrosilylation, hydroboration, hydroalumination and terminal metalation based on group 13 and 14 elements. In the case of terminal alkyne metalation, the Lewis-acidic gallium function was introduced using triethylgallium under alkane elimination. A total of six different Lewis acids based on a semiflexible organic scaffold were prepared, bearing -SiClMe , -SiCl Me, -SiCl , -B(C F ) , -AlBis (Bis=bis(trimethylsilyl)methyl) and -GaEt as the corresponding functional units.
View Article and Find Full Text PDFSynthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes ethyl and amide zinc thioureides.
Chem Sci
July 2021
Materials Chemistry Centre, Department of Chemistry, University College London 20 Gordon Street London WC1H 0AJ UK
Ethyl and amide zinc thioureides [LZnEt] (), [L*ZnEt] () and [LZn(N(SiMe))] () have been synthesised from the equimolar reaction of thiourea ligands (HL = PrN(H)CSNMe and HL* = PhN(H)CSNMe) with diethyl zinc and zinc bis[bis(trimethylsilyl)amide] respectively. New routes towards heteroleptic complexes have been investigated through reactions of , and with β-ketoiminates (HL = [(Me)CN(H){Pr}-CHC(Me)[double bond, length as m-dash]O]), bulky aryl substituted β-diiminates (HL = [(Me)CN(H){Dipp}-CHC(Me)[double bond, length as m-dash]N{Dipp}] (Dipp = diisopropylphenyl) and HL* = [(Me)CN(H){Dep}-CHC(Me)[double bond, length as m-dash]N{Dep}] (Dep = diethylphenyl)) and donor-functionalised alcohols (HL = EtN(CH)OH and HL* = MeN(CH)OH) and have led to the formation of the heteroleptic complexes [L*ZnL*] (), [LZnL] (), [LZnL*] (), [L*ZnL] () and [L*ZnL*] (). All complexes have been characterised by H and C NMR, elemental analysis, and the X-ray structures of HL*, , , and have been determined single crystal X-ray diffraction.
View Article and Find Full Text PDFSynthesis, C-H bond functionalisation and cycloadditions of 6-styryl-1,2-oxathiine 2,2-dioxides.
Org Biomol Chem
July 2021
Department of Chemical Sciences, School of Applied Sciences, University of Huddersfield, Queensgate, Huddersfield, HD1 3DH, UK.
A series of 6-styryl-1,2-oxathiine 2,2-dioxides have been efficiently obtained by a two-step protocol from readily available (1E,4E)-1-(dimethylamino)-5-arylpenta-1,4-dien-3-ones involving a regioselective sulfene addition and subsequent Cope elimination. Pd-Mediated direct C-H bond functionalisation of the 6-styryl-1,2-oxathiine 2,2-dioxides and a wider selection of 5,6-diaryl substituted 1,2-oxathiine 2,2-dioxides proceeded smoothly to afford C-3 (hetero)aryl substituted analogues and the results are contrasted with those of a complementary bromination - Suzuki cross-coupling sequence. Whilst the cycloaddition of benzyne, derived from in situ fluoride initiated decomposition of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, to the substituted 1,2-oxathiine 2,2-dioxides resulted in low yields of substituted naphthalenes, the addition of 4-phenyl-1,2,4-triazoline-3,5-dione to the 6-styryl-1,2-oxathiine 2,2-dioxides afforded novel 5,9-dihydro-1H-[1,2]oxathiino[5,6-c][1,2,4]triazolo[1,2-a]pyridazine-1,3(2H)-dione 8,8-dioxides through a silica-mediated isomerisation of the initial [4 + 2] adducts.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!