TY - JOUR
T1 - Synthesis, structure, and reactions of binuclear gold(I) complexes containing two different bridging ligands
AU - Bhargava, S. K.
AU - Mohr, F.
AU - Bennett, M. A.
AU - Welling, L. L.
AU - Willis, A. C.
PY - 2001/8/13
Y1 - 2001/8/13
N2 - The binuclear cycloaurated compounds [Au2(μ-C6H3-2-PPh2-n-Me) 2] (n = 5, 1a; n = 6, 1b) react with the digold-(I) complexes [Au2(μ-S2CNnBu2)2] and [Au2(μ-dppm)2](PF6)2 to give heterobridged dinuclear complexes [Au2- (μ-C6H3-2-PPh2-n-Me)(μ-S2 CNnBu2 (n = 5, 5a; n = 6, 5b) and [Au2(μ-C6H3-2-PPh2-n-Me) (μ-dppm)]PF6, (n = 5, 9a; n = 6, 9b), respectively. Complex 5a exists in the solid state as an infinite zigzag chain of dimeric units with intramolecular Au-Au separations of 2.8331(3) and 2.8243(3) Å for independent molecules and intermolecular Au-Au separations of 3.0653(3) and 3.1304(3) Å. Both 5a and 5b undergo oxidative addition with halogens to give the heterovalent, gold(I)-gold(III) compounds [XAuI(μ-2-Ph2PC6H3-n-Me) AuIIIX(η2-S2CNn Bu2) [n = 5, X = Cl (6a), I (8a); n = 6, X = Cl (6b), Br (7b), I (8b)]. Compound 8a has been shown by X-ray crystallography to contain a gold(III) atom coordinated in a planar array by bidentate, chelating di-n-butyldithiocarbamate, iodide, and the σ-aryl carbon atom, together with a gold(I) atom that is linearly coordinated by the phosphorus atom of the arylphosphine and by iodide. The intramolecular gold-gold distance of 3.2201(3) Å indicates little or no interaction between the metal atoms. In contrast to the behavior of the homobridged complexes 1a and 1b, the heterobridged dithiocarbamate complexes 5a and 5b give structurally similar products on reaction with halogens, irrespective of the position of the ring methyl substituent. Crystal data for [Au2(μ-C6H3-2-PPh2-5-Me) (μ-S2CNn-Bu2)] (5a): triclinic, space group P1̄ (No. 2), with a = 11.3398(1), b = 15.9750(2), c = 16.4400(3) Å α = 91.0735(9), β = 109.3130(7), γ = 90.7666(8)° V = 2809.47(6) Å3, and Z = 4. Crystal data for [IAuI(μ-2-Ph2-PC6H3-5-Me) AuIIII(η2- S2CNnBu2)] (8a): triclinic, space group P1̄ (No. 2), with a = 8.6136(2), b = 9.3273, c = 21.1518(4) Å, α = 84.008(1), β = 84.945(1), γ = 75.181(1)°, V = 1630.54(6) Å3, and Z = 2.
AB - The binuclear cycloaurated compounds [Au2(μ-C6H3-2-PPh2-n-Me) 2] (n = 5, 1a; n = 6, 1b) react with the digold-(I) complexes [Au2(μ-S2CNnBu2)2] and [Au2(μ-dppm)2](PF6)2 to give heterobridged dinuclear complexes [Au2- (μ-C6H3-2-PPh2-n-Me)(μ-S2 CNnBu2 (n = 5, 5a; n = 6, 5b) and [Au2(μ-C6H3-2-PPh2-n-Me) (μ-dppm)]PF6, (n = 5, 9a; n = 6, 9b), respectively. Complex 5a exists in the solid state as an infinite zigzag chain of dimeric units with intramolecular Au-Au separations of 2.8331(3) and 2.8243(3) Å for independent molecules and intermolecular Au-Au separations of 3.0653(3) and 3.1304(3) Å. Both 5a and 5b undergo oxidative addition with halogens to give the heterovalent, gold(I)-gold(III) compounds [XAuI(μ-2-Ph2PC6H3-n-Me) AuIIIX(η2-S2CNn Bu2) [n = 5, X = Cl (6a), I (8a); n = 6, X = Cl (6b), Br (7b), I (8b)]. Compound 8a has been shown by X-ray crystallography to contain a gold(III) atom coordinated in a planar array by bidentate, chelating di-n-butyldithiocarbamate, iodide, and the σ-aryl carbon atom, together with a gold(I) atom that is linearly coordinated by the phosphorus atom of the arylphosphine and by iodide. The intramolecular gold-gold distance of 3.2201(3) Å indicates little or no interaction between the metal atoms. In contrast to the behavior of the homobridged complexes 1a and 1b, the heterobridged dithiocarbamate complexes 5a and 5b give structurally similar products on reaction with halogens, irrespective of the position of the ring methyl substituent. Crystal data for [Au2(μ-C6H3-2-PPh2-5-Me) (μ-S2CNn-Bu2)] (5a): triclinic, space group P1̄ (No. 2), with a = 11.3398(1), b = 15.9750(2), c = 16.4400(3) Å α = 91.0735(9), β = 109.3130(7), γ = 90.7666(8)° V = 2809.47(6) Å3, and Z = 4. Crystal data for [IAuI(μ-2-Ph2-PC6H3-5-Me) AuIIII(η2- S2CNnBu2)] (8a): triclinic, space group P1̄ (No. 2), with a = 8.6136(2), b = 9.3273, c = 21.1518(4) Å, α = 84.008(1), β = 84.945(1), γ = 75.181(1)°, V = 1630.54(6) Å3, and Z = 2.
UR - http://www.scopus.com/inward/record.url?scp=0035854966&partnerID=8YFLogxK
U2 - 10.1021/ic010272i
DO - 10.1021/ic010272i
M3 - Article
SN - 0020-1669
VL - 40
SP - 4271
EP - 4275
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 17
ER -