Structural Diversity in Molecular Nickel Phosphide Carbonyl Nanoclusters

Abstract

The reaction of [Ni6(CO)12]2– as a [NBu4]+ salt in CH2Cl2 with 0.8 equiv of PCl3 afforded [Ni14P2(CO)22]2–. In contrast, the reactions of [Ni6(CO)12]2– as a [NEt4]+ salt with 0.4–0.5 equiv of POCl3 afforded [Ni22–x P2(CO)29–x ]4– (x = 0.84) or [Ni39P3(CO)44]6– by using CH3CN and thf as a solvent, respectively. Moreover, by using 0.7–0.9 mol of POCl3 per mole of [NEt4]2[Ni6(CO)12] both in CH3CN and thf, [Ni23–x P2(CO)30–x ]4– (x = 0.82) was obtained together with [Ni22P6(CO)30]2– as a side product. [Ni23–x P2(CO)30–x ]4– (x = 0.82) and [Ni22P6(CO)30]2– were separated owing to their different solubility in organic solvents. All the new molecular nickel phosphide carbonyl nanoclusters were structurally characterized through single crystal X-ray diffraction (SC-XRD) as [NBu4]2[Ni14P2(CO)22] (two different polymorphs, P21/n and C2/c), [NEt4]4[Ni23–x P2(CO)30–x ]·CH3COCH3·solv (x = 0.82), [NEt4]2[Ni22P6(CO)30]·2thf, [NEt4]4[Ni22–x P2(CO)29–x ]·2CH3COCH3( x = 0.84) and [NEt4]6[Ni39P3(CO)44]·C6H14·solv. The metal cores’ sizes of these clusters range from 0.59 to 1.10 nm, and their overall dimensions including the CO ligands are 1.16–1.63 nm. In this respect, they are comparable to ultrasmall metal nanoparticles, molecular nanoclusters, or atomically precise metal nanoparticles. The environment of the P atoms within these molecular Ni–P–CO nanoclusters displays a rich diversity, that is, Ni5P pentagonal pyramid, Ni7P monocapped trigonal prism, Ni8P bicapped trigonal prism, Ni9P monocapped square antiprism, Ni10P sphenocorona, Ni10P bicapped square antiprism, and Ni12P icosahedron.

Atomically Precise Ni–Pd Alloy Carbonyl Nanoclusters: Synthesis, Total Structure, Electrochemistry, Spectroelectrochemistry, and Electrochemical Impedance Spectroscopy

“…Even if the empirical parameter x is within a wide range, it displays similar values for related clusters. Thus, for Ni–Pd carbonyl clusters, x is between 7 and 11, ,− whereas it can reach higher values in the case of HNMCCs containing interstitial main group atoms such as phosphides and carbides. , …”

“…Thus, for Ni–Pd carbonyl clusters, x is between 7 and 11, 14 , 45 − 47 whereas it can reach higher values in the case of HNMCCs containing interstitial main group atoms such as phosphides and carbides. 51 , 52…”

“…Thus, for Ni−Pd carbonyl clusters, x is between 7 and 11, 14,45−47 whereas it can reach higher values in the case of HNMCCs containing interstitial main group atoms such as phosphides and carbides. 51,52 The presence of substitutional and compositional disorder in Ni−Pd carbonyl clusters is further exemplified by the structures of 2 6− and 3 5− (Figure 3, Table 1, and Figures S1 and S2). The related [Ni 36 Pd 8 (CO) 48 ] 6− anion has been previously reported.…”

From M6 to M12, M19 and M38 molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

“…Indeed, Ni(CO) fragments are often found capping triangular faces in several clusters. [49][50][51] The M-M bonding contacts of [Pt 19−x Ni x (CO) 22 ] 4− (x = 2.23, 3.11, 5.26) can be divided into eight groups, as depicted in Table 5 (see Scheme 3 for labeling). The general trends observed among the different groups are similar to those reported for the homometallic cluster [Pt 19 (CO) 22 ] 4− , 38 that is,…”

Metal Nanoclusters in Point-of-Care Sensing and Biosensing Applications

“…In this study, Zn was anchored on the surface of the NCs to enhance the adsorption capability of the system to increase its sensing ability toward CO 2 . Other phosphide NCs have been introduced through experimental and/or theoretical concepts. − A substantial shortage of phosphide NCs is comparing them with phosphide nanoparticles in terms of optical, electrical, and catalytical aspects. This could brighten the road for further studies and application of these NCs in sensing and biosensing assays.…”