TY - JOUR
T1 - Rhenium complexes with di- and tri-thiolate ligands. The synthesis and X-ray crystal structures of square pyramidal [PPh4][ReO(SCH2CH2S)2] and [NMe4][ReS(SCH2CH2S)2] and trigonal prismatic [PPh4][Re{(SCH2)3CCH3}2]
AU - Blower, Philip J.
AU - Dilworth, Jonathan R.
AU - Hutchinson, John P.
AU - Nicholson, Terence
AU - Zubieta, Jon
PY - 1986
Y1 - 1986
N2 - The complexes [PPh4] [ReO(SCH2CH2S)2] (1), [NMe4] [ReS(SCH2CH2S)2] (3), and [PPh4] [Re{(SCH2)3CCH3}2] (5) have been synthesised by the reactions of K2[ReCl6] or [ReOCl3(PPh3)2] with the respective polythiol in the presence of triethylamine in methanol solution. Complex (1) crystallises in space group Pcab with a = 15.122(3), b = 18.685(4), c = 19.648(4) Å, U = 5 542.02 Å3, and Z = 4. Structure solution based on 2 072 independent reflections was refined to R = 0.063. Complex (3) crystallises in space group P21/c with a = 9.539(3), b = 15.123(4), c = 21.815(4) Å, β = 93.58(1)°, U = 3 140.9 Å3, and Z = 8. Structure solution based on 3 329 independent reflections was refined to R = 0.029. Complex (5) crystallises in space group P21/n with a = 11.506(3), b = 17.096(4), c = 18.115(4) Å, β = 102.32(1)°, U = 3 488.9 Å3, and Z = 4. Structure solution based on 2 380 independent reflections was refined to R = 0.0517. The [ReS(SCH2CH2S)2]- and [ReO(SCH2CH2S)2]- anions exhibit square pyramidal geometry with a terminal sulphido or oxo ligand in the apical position. The S2- ligand is derived from decomposition of the 1,2-ethanedithiolate anion with elimination of ethylene. The [Re{(SCH2)3CCH3}2]- anion has a six-co-ordinate Re atom in a trigonal prismatic co-ordination sphere. The factors responsible for the adoption of the trigonal prismatic structure are discussed.
AB - The complexes [PPh4] [ReO(SCH2CH2S)2] (1), [NMe4] [ReS(SCH2CH2S)2] (3), and [PPh4] [Re{(SCH2)3CCH3}2] (5) have been synthesised by the reactions of K2[ReCl6] or [ReOCl3(PPh3)2] with the respective polythiol in the presence of triethylamine in methanol solution. Complex (1) crystallises in space group Pcab with a = 15.122(3), b = 18.685(4), c = 19.648(4) Å, U = 5 542.02 Å3, and Z = 4. Structure solution based on 2 072 independent reflections was refined to R = 0.063. Complex (3) crystallises in space group P21/c with a = 9.539(3), b = 15.123(4), c = 21.815(4) Å, β = 93.58(1)°, U = 3 140.9 Å3, and Z = 8. Structure solution based on 3 329 independent reflections was refined to R = 0.029. Complex (5) crystallises in space group P21/n with a = 11.506(3), b = 17.096(4), c = 18.115(4) Å, β = 102.32(1)°, U = 3 488.9 Å3, and Z = 4. Structure solution based on 2 380 independent reflections was refined to R = 0.0517. The [ReS(SCH2CH2S)2]- and [ReO(SCH2CH2S)2]- anions exhibit square pyramidal geometry with a terminal sulphido or oxo ligand in the apical position. The S2- ligand is derived from decomposition of the 1,2-ethanedithiolate anion with elimination of ethylene. The [Re{(SCH2)3CCH3}2]- anion has a six-co-ordinate Re atom in a trigonal prismatic co-ordination sphere. The factors responsible for the adoption of the trigonal prismatic structure are discussed.
UR - http://www.scopus.com/inward/record.url?scp=37049083270&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=37049083270&partnerID=8YFLogxK
U2 - 10.1039/DT9860001339
DO - 10.1039/DT9860001339
M3 - Article
AN - SCOPUS:37049083270
SN - 1472-7773
SP - 1339
EP - 1345
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 7
ER -