Omar M. Abu-Salah

Perspectives in syntheses, structures and bonding of acetylide-containing clusters of group 11 metals

Abstract New aspects of chemistry and bonding have emerged from reactions of the anionic linear complexes [M(C 2 Ph) 2 ] − with metal phenylacetylide polymers [M(C 2 Ph)] n (M=Cu, Ag, Au). The reactions did not stop at depolymerization, but were followed by ethynylation and condensation of the formed cationic and anionic moieties into novel clusters. Thus the homonuclear [Ag 5 (C 2 Ph) 6 ] − and hetreonuclear [Au 2 Cu(C 2 Ph) 4 ] − , [Au 3 M 2 (C 2 Ph) 6 ] − (M=Cu, Ag), [Ag 6 Cu 7 (C 2 Ph) 14 ] − , and [AuAg 6 Cu 6 (C 2 Ph) 14 ] − complexes were obtained. Extension of ethynylation reactions to neutral complexes resulted in the complexes [Au 2 Ag 2 (C 2 Ph) 4 (PPh 3 ) 2 ], [Ag 2 Cu 2 (C 2 Ph) 4 (PPh 3 ) 4 ], [AuAg(C 2 Ph) 2 ] n , [AuCu(C 2 Ph) 2 ] n , and [AgCu(C 2 Ph) 2 ] n . Aspects of syntheses, structures and bonding in these complexes are reviewed.

Preparation, identification, and X-ray structure of a novel pentanuclear gold–copper cluster complex

The reaction of [NBun4][PhC2AuC2Ph] with a mixture of [AuC2Ph]n and [CuC2Ph]n yield mainly the pentanuclear cluster [NBun4][Au3Cu2(C2Ph)6].

A new class of cluster complexes between group IB metal arylacetylides. Preparation and x-ray structure of a novel tetranuclear gold-silver cluster

Abstract The cluster [Au 2 Ag 2 (C 2 Ph) 4 (PPh 3 ) 2 )] has been prepared by the reaction of Ph 3 PAuC 2 Ph with [AgC 2 Ph] n , and by that of Ph 3 P with the polymer [AuAg(C 2 Ph) 2 ] n . The structure of the new cluster involves a linear arrangement of two phenylacetylide groups about each gold atom, with each silver atom asymmetrically π-bonded to two triple bonds and one phosphine ligand.

Syntheses and reactivity of acetylide-containing clusters of group 1B metals VII. Preparation and possible structures of the novel pentanuclear [Au3Ag2(C2Ph)6]−, [Ag5(C2Ph)6]−, and [Ag4Cu(C2Ph)6]− clusters. The reactivity of the polymer complexes [{AuAg(C2Ph)2}n] and [{AuCu(C2Ph)2}n]

Abstract The stepwise synthesis of the gold-silver pentanuclear cluster [Au 3 Ag 2 (C 2 Ph) 6 ] − is described. The pentanuclear clusters [Ag 5 (C 2 Ph) 6 ] − and [Ag 4 Cu(C 2 Ph) 6 ] − are obtained by the reactions of silver phenylacetylide with, respectively, the linear silver complex anion [Ag(C 2 Ph) 2 ] − and with its copper analogue. Their possible structures are discussed. Depending on the molar ratio of the reactants, the reaction of [Cu(C 2 Ph) 2 ] − and [{AuCu(C 2 Ph) 2 } n ] affords the cluster [Au 2 Cu(C 2 Ph) 4 ] − or the complex [Au 3 Cu 2 (C 2 Ph) 6 ] − . Whereas the reaction of [Cu(C 2 Ph) 2 ] − and [{AuAg(C 2 Ph) 2 } n ] gives [Au 3 Ag 2 (C 2 Ph) 6 ] − and the trimetallic complex [AuAg 6 Cu 6 (C 2 Ph) 14 ] − , that between [Ag(C 2 Ph) 2 ] − and the same polymer complex affords only [Au 3 Ag 2 (C 2 Ph) 6 ] − .

Syntheses and reactivity of acetylide-containing clusters of Group IB metals. Preparation, structure, and reactions of the tetranuclear cluster [Au2Ag2(C2Ph)4(PPh3)2]. Syntheses and structure of the novel mixed-metal gold-silver and gold-copper phenylacetylide polymer complexes [{AuM(C2Ph)2}n] (M = Ag, Cu)

Abstract The tetranuclear cluster [Au2Ag2(C2Ph)4(PPh3)2] has been made by reaction of [Au(C2Ph)PPh3] with [{Ag(C2Ph)}n] ( 1 1 ). Its structure and reactions are described. The novel mixed gold-silver and gold-copper phenylacetylide polymers [{AuM(C2Ph)2}n] (M = Ag, Cu) have been made by reaction of [Au(C2Ph)L] (L = AsPh3, P(OPh)3) with [{Ag(C2Ph)}n] and [{Cu(C2Ph)}n]. The gold-silver polymer has also been made by reaction of [AuClPPh3] with [{Ag(C2Ph)}n] ( 1 2 ). The structures of the polymers are discussed.

The synthesis, identification, and X-ray structure of a novel cationic alkynyl silver cluster polymer [Ag3(C2But)2+]n

Abstract The reaction between AgBF4 and [Ag(C2But)]n in 1:2 mol ratio affords the novel cationic polymer [Ag3(C2But)2+]n. The crystal structure has been determined by single-crystal X-ray diffraction study.

Syntheses and reactivity of acetylide-containing clusters of Group 1B metals: VIII Preparation, characterization and possible structure of a novel pentanuclear trimetallic cluster [Au3AgCu(C2Ph)6]−. Reactions of pentanuclear and trinuclear acetylide complexes☆

Abstract The novel pentanuclear trimetallic cluster [Au 3 AgCu(C 2 Ph) 6 ] − has been prepared by the reactions of [Au 3 Cu 2 (C 2 Ph) 6 ] − with a mixture of gold phenylacetylide and silver phenylacetylide, of [Au 3 Ag 2 (C 2 Ph) 6 ] − with [AuCu(C 2 Ph) 2 n ], or of [Au 2 Cu(C 2 Ph) 4 ] − with [AuAg(C 2 Ph) 2 n ]. Its possible structure is discussed. The conversion of the pentanuclear clusters [Au 3 Cu 2 (C 2 Ph) 6 ] − and [Au 3 Ag 2 (C 2 Ph) 6 ] − into the high polynuclearity trimetallic cluster [AuAg 6 Cu 6 (C 2 Ph) 14 ] − and of [Ag 4 Cu(C 2 Ph) 6 ] − into the complex [Ag 6 Cu 7 (C 2 Ph) 14 ] − is described. The reactions of [Au 2 Cu(C 2 Ph) 4 ] − with PPh 3 , P(OMe) 3 , and CuCl, and those of [Au 2 CuCl(C 2 Ph) 4 ] 2− with [AuCu(C 2 Ph) 2 n ], a mixture of [Ag(C 2 Ph) n ] and V76 [Cu(C 2 Ph) n ], and CuCl are reported.

[N(PPh3)2]2[{Au3Ag2(C2Ph)6} {Au3Cu2(Cu2Ph)6}]: Co-crystallized pentanuclear bimetallic gold-silver and gold-copper clusters

The X-ray structural study of the reaction product of equimolar amounts of [Au3Cu2(C2Ph)6]. [{Au(C2Ph)}n], and [Ag(C2Ph)}n] revealed two bimetallic anionic [N(PPh3)2] + [Au3Ag2(C2Ph)6]− and [N(PPh3)2]+[Au3Cu2 (C2 Pg)6] — clusters co-crystallized in one asymmetric unit. Each cluster has trigonal bipyramidal geometry with three gold atoms occupying equatorial planes and two silver or copper atoms in the apical positions. Our earlier conclusion based upon spectroscopic characterization describing the product of be above reaction as trimetallic cluster containing three coinage-metals with an overall composition [Au3CuAg(C2Ph)6]−, was erroneous.

Syntheses and reactivity of acetylide-containing clusters of group 1B metals. Preparation and identification of the novel bimetallic [Ag6Cu7(C2Ph)14]− and the analogous trimetallic [AuAg6Cu6(C2Ph)14]− clusters

Abstract The reaction of the linear complex [Ag(C 2 Ph) 2 ] − and a mixture of [{Cu(C 2 Ph)} n ] and [{Ag(C 2 Ph)} n ] afforded the novel heteronuclear cluster [Ag 6 Cu 7 (C 2 Ph) 14 ] − ( 1 ). The same cluster was obtained when [Cu(C 2 Ph) 2 ] − or halide ions, X − (X = Cl, Br, I), were treated with a mixture of the same polymer complexes. The analogous trimetallic complex [AuAg 6 Cu 6 (C 2 Ph) 14 ] − was the sole cluster obtained when [Au(C 2 Ph) 2 ] − was employed in different mole ratios with the above mixture of polymers. Some structural data for the two complexes are discussed.

A novel high nuclearity bimetallic cluster: The crystal structure of [N(PPh3)2][Ag6Cu7(C2Ph)14]

Abstract An X-ray diffraction study of the high nuclearity complex [N(PPh 3 ) 2 ][Ag 6 Cu 7 (C 2 Ph) 14 ] has shown it to be a novel 13-atom bimetallic anionic cluster [Ag 6 Cu 7 (C 2 Ph) 14 ] − with two types of copper atoms, one inside the body of the cluster and six on its surface. The surface atoms have a distorted trigonal bipyramidal geometry whereas the internal copper atom is linearly coordinated by two C 2 Ph groups in addition to displaying six CuAg bonding interactions with three tetranuclear [Ag 2 Cu 2 (C 2 Ph) 4 ] subclusters. Thus the internal copper atom essentially exhibits eight-coordination. All the silver atoms have a bent two-coordinate geometry as far as CuAgCu metal bonding is concerned. These atoms are also asymmetrically π bonded to alkyne groups on the phenyl moieties attached to the adjacent copper atoms. This complex represents a new class of Group 1B metal clusters with a bonding pattern not observed previously.