Syntheses and structures of the heterometallic clusters [(Ph 3PAu) 3Re(CO) 4], [(Ph 3PAu) 4Re(CO) 4] +, [(Ph 3PAu) 6AuRe 2(CO) 8] +, and [(Ph 3PAu) 6Re(CO) 3]

• Published in: Inorganica Chimica Acta Vol. 358; no. 14; pp. 4301 - 4306
• Main Authors: Pivoriunas, G., Richter, M., Strähle, J.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-11-2005
• Subjects: Crystal structure; Heterometallic gold rhenium clusters; Synthesis; Heterometallic gold rhenium clusters; Synthesis; Crystal structure
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2005.02.022

The new heterometallic rhenium gold clusters [(Ph
3PAu)
3Re(CO)
4], [(Ph
3PAu)
4Re(CO)
4]
+, [(Ph
3PAu)
6AuRe
2(CO)
8]
+, and [(Ph
3PAu)
6Re(CO)
3]
+ have been synthesized and structurally characterized.[(Ph
3PAu)
4Re(CO)
4]
+ is obtained from [HRe
3(CO)
12]
2− and Ph
3PAuCl.It reacts with Cl
− to yield the neutral cluster [(Ph
3PAu)
3Re(CO)
4] and Ph
3PAuCl.[(Ph
3PAu)
3Re(CO)
4] and [(Ph
3PAu)
4Re(CO)
4]
+ condense to form the larger cluster [(Ph
3PAu)
6AuRe
2(CO)
8]
+.The famous base reaction is used to obtain [(Ph
3PAu)
6Re(CO)
3]
+ from [(Ph
3PAu)
4Re(CO)
4]
+, Ph
3PAu
+ and OH
−.
The reaction of [HRe
3(CO)
12]
2− with an excess of Ph
3PAuCl in CH
2Cl
2 yields [(Ph
3PAu)
4Re(CO)
4]
+ as the main product, which crystallizes as [(Ph
3PAu)
4Re(CO)
4]PF
6
·
CH
2Cl
2 (
1
·
CH
2Cl
2) after the addition of KPF
6.The crystal structure determination reveals a trigonal bipyramidal Au
4Re cluster with the Re atom in equatorial position.
If [(Ph
3PAu)
4Re(CO)
4]
+ is reacted with PPh
4Cl, a cation [Ph
3PAu]
+ is eliminated as Ph
3PAuCl, and the neutral cluster [(Ph
3PAu)
3Re(CO)
4] (
2) is formed.It combines with excess [(Ph
3PAu)
4Re(CO)
4]
+ to afford the cluster cation, [(Ph
3PAu)
6AuRe
2(CO)
8]
+.
It crystallizes from CH
2Cl
2 as[(Ph
3PAu)
6AuRe
2(CO)
8]PF
6
·
4CH
2Cl
2 (
3
·
4CH
2Cl
2). In [(Ph
3PAu)
3Re(CO)
4] the metal atoms are arranged in form of a lozenge while in [(Ph
3PAu)
6AuRe
2(CO)
8]
+ two Au
4Re trigonal bipyramids are connected by a common axial Au atom.
The treatment of [(Ph
3PAu)
4Re(CO)
4]
+ with KOH and Ph
3PAuCl in methanol yields the cluster cation [(Ph
3PAu)
6Re(CO)
3]
+, which crystallizes with
PF
6
-
from CH
2Cl
2 as [(Ph
3PAu)
6Re(CO)
3]PF
6
·
CH
2Cl
2 (
4
·
CH
2Cl
2). The metal atoms in this cluster form a pentagonal bipyramid with the Re atom in the axial position.