Cluster Core Isomerism Induced by Crystal Packing Effects in the [HCoPdC(CO)] Molecular Nanocluster.

This article describes a rare case of cluster core isomerism in a large molecular organometallic nanocluster. In particular, two isomers of the [HCoPdC(CO)] nanocluster, referred as TP-Pd and Oh-Pd, have been structurally characterized by single-crystal X-ray crystallography as their [NMe(CHPh)][HCoPdC(CO)]·CHCl (ca. 1:1 TP-Pd and Oh-Pd mixture), [NMe(CHPh)][HCoPdC(CO)]·2CHCl (mainly TP-Pd), [NEt(CHPh)][HCoPdC(CO)]·CHCl (mainly TP-Pd), [MePPh][HCoPdC(CO)]·2.

Synthesis of [Pt(CO)(dppm)] and [Pt(CO)(dppm)] Heteroleptic Chini-type Platinum Clusters by the Oxidative Oligomerization of [Pt(CO)(dppm)].

The reactions of [Pt(CO)] with CH(PPh) (dppm), CH═C(PPh) (P^P), and Fe(CHPPh) (dppf) proceed via nonredox substitution and result in the heteroleptic Chini-type clusters [Pt(CO)(dppm)], [Pt(CO)(P^P)], and [Pt(CO)(dppf)], respectively. Conversely, the reactions of [Pt(CO)] with PhP(CH)PPh (dppb) and PhPC≡CPPh (dppa) can be described as redox fragmentation that afford the neutral complexes Pt(dppb), Pt(CO)(dppa), and Pt(CO)(PPh)(C≡CPPh)(dppa). The oxidation of [Pt(CO)(dppm)] results in its oligomerization to yield the larger heteroleptic Chini-type clusters [Pt(CO)(dppm)], [Pt(CO)(dppm)], and [Pt(CO)(dppm)] (for the latter there is only IR spectroscopic evidence).

Water soluble derivatives of platinum carbonyl Chini clusters: synthesis, molecular structures and cytotoxicity of [Pt(CO)(PTA)] and [Pt(CO)(PTA)] .

The reactions of [Pt3n(CO)6n]2- (n = 2-5) homoleptic Chini-type clusters with increasing amounts of 1,3,5-triaza-7-phosphaadamantane (PTA) result in the stepwise substitution of one terminal CO ligand per Pt3 triangular unit up to the formation of [Pt3n(CO)5n(PTA)n]2- (n = 2-5). Competition between the nonredox substitution with retention of the nuclearity and the redox fragmentation to afford lower nuclearity heteroleptic Chini-type clusters is observed as a function of the amount of PTA and the nuclearity of the starting cluster. Because of this, [Pt12(CO)20(PTA)4]2- and [Pt15(CO)25(PTA)5]2- are more conveniently obtained via the oxidation of [Pt9(CO)15(PTA)3]2-.

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [NiP(CO)] and [HNiP(CO)] (n = 4 and 5).

The reaction of [NEt][Ni(CO)] in thf with 0.5 equiv of PCl affords the monophosphide [NiP(CO)] that in turn further reacts with PCl resulting in the tetra-phosphide carbonyl cluster [HNiP(CO)]. Alternatively, the latter can be obtained from the reaction of [NEt][Ni(CO)] in thf with 0.

Interstitial Bismuth Atoms in Icosahedral Rhodium Cages: Syntheses, Characterizations, and Molecular Structures of the [Bi@Rh(CO)], [(Bi@Rh(CO))Bi], [Bi@Rh(CO)Bi], and [Bi@Rh(CO)Bi] Carbonyl Clusters.

The reaction of [Rh(CO)] with BiCl under N and at room temperature results in the formation of the new heterometallic [Bi@Rh(CO)] cluster in high yields. Further controlled addition of BiCl leads first to the formation of the dimeric [(Bi@Rh(CO))Bi] and the closo-[Bi@Rh(CO)Bi] species in low yields, and finally, to the [Bi@Rh(CO)Bi] cluster. All clusters were spectroscopically characterized by IR and electrospray ionization mass spectrometry, and their molecular structures were fully determined by X-ray diffraction studies.