TY - JOUR
T1 - Gold(I) complexes with P=O and P-OH functionalised phosphorus ligands
AU - Hollatz, Christian
AU - Schier, Annette
AU - Schmidbaur, Hubert
PY - 2000/4/30
Y1 - 2000/4/30
N2 - P-coordination of anionic phosphonite [(R2O)R1PO]- or phosphite [(RO)2PO]- ligands to (triorganophosphine)gold(I) units leads to neutral molecules with an unsymmetrical P-Au-P' axis and a P=O function. A general synthetic route starts from (R3P)AuMe precursors and the corresponding primary phosphonites (R2O)R1P(O)H or secondary phosphites (RO)2P(O)H, respectively. The gold(I) phosphonites (R3P)AuP(O)R1(OR2) (1a-d) undergo a ligand redistribution in solution, establishing equilibria that involve ionic isomers of the type [(R3P)2Au]+[Au{P(O)R1(OR2)}2]- as demonstrated by NMR spectroscopy. In the complexes Ph2P(OH)AuCl (2), Ph2P(OH)AuGeCl3 (3), [Ph2P(OH)]2Au+X-, with X- = ClO4- (4a), SbF6- (4b), BF4- (4c), TfO-(4d) and (MeO)2P(OH)AuCl (5) the phosphinous acid and the phosphorous acid diester, respectively, are coordinated to gold(I) as neutral ligands with a P-OH function, respectively. The combination of the anionic phosphite and neutral ester ligands in the same molecule leads to the formation of compounds [(RO)2P(OH)AuP(O)(OR)2](n) (6a-c), which oligomerise via cooperative action of hydrogen and aurophilic bonding as determined by single-crystal X-ray diffraction and NMR measurements. The degree of oligomerisation depends largely on the steric effect of the R groups. Compound 6b is a dimer, while compound 6a is a polymer. The crystal structure of the phosphite complex [(Me3P)AuP(O)(OMe)2](n) (7) contains a chain of neutral monomeric units associated solely via aurophilic contacts. (C) 2000 Elsevier Science S.A.
AB - P-coordination of anionic phosphonite [(R2O)R1PO]- or phosphite [(RO)2PO]- ligands to (triorganophosphine)gold(I) units leads to neutral molecules with an unsymmetrical P-Au-P' axis and a P=O function. A general synthetic route starts from (R3P)AuMe precursors and the corresponding primary phosphonites (R2O)R1P(O)H or secondary phosphites (RO)2P(O)H, respectively. The gold(I) phosphonites (R3P)AuP(O)R1(OR2) (1a-d) undergo a ligand redistribution in solution, establishing equilibria that involve ionic isomers of the type [(R3P)2Au]+[Au{P(O)R1(OR2)}2]- as demonstrated by NMR spectroscopy. In the complexes Ph2P(OH)AuCl (2), Ph2P(OH)AuGeCl3 (3), [Ph2P(OH)]2Au+X-, with X- = ClO4- (4a), SbF6- (4b), BF4- (4c), TfO-(4d) and (MeO)2P(OH)AuCl (5) the phosphinous acid and the phosphorous acid diester, respectively, are coordinated to gold(I) as neutral ligands with a P-OH function, respectively. The combination of the anionic phosphite and neutral ester ligands in the same molecule leads to the formation of compounds [(RO)2P(OH)AuP(O)(OR)2](n) (6a-c), which oligomerise via cooperative action of hydrogen and aurophilic bonding as determined by single-crystal X-ray diffraction and NMR measurements. The degree of oligomerisation depends largely on the steric effect of the R groups. Compound 6b is a dimer, while compound 6a is a polymer. The crystal structure of the phosphite complex [(Me3P)AuP(O)(OMe)2](n) (7) contains a chain of neutral monomeric units associated solely via aurophilic contacts. (C) 2000 Elsevier Science S.A.
KW - Crystal structures
KW - Gold complexes
KW - Phosphite complexes
KW - Phosphonite complexes
UR - https://www.scopus.com/pages/publications/0034732483
U2 - 10.1016/S0020-1693(99)00459-4
DO - 10.1016/S0020-1693(99)00459-4
M3 - Article
AN - SCOPUS:0034732483
SN - 0020-1693
VL - 300-302
SP - 191
EP - 199
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -