An ab initio study of structures and energetics of copper sulfide clusters

Chemistry - A European Journal

Volumn 2, Issue 4, 1996, Pages 429-435

  Dehnen, Stefanie ^a   Schäfer, Ansgar ^b   Ahlrichs, Reinhart ^b   Fenske, Dieter ^a  

^a Universitat   (Germany)

^b UNIVERSITY OF KARLSRUHE   (Germany)

Author keywords

Ab initio calculations; Chalcogen compounds; Copper clusters; Ligand stabilisation; Thermodynamics

Indexed keywords

AB INITIO CALCULATIONS; ACTIVATION ENERGY OF DECOMPOSITION; CHALCOGENS; COPPER CLUSTER; FORMAL SUBSTITUTION; TERTIARY PHOSPHINES; THEORETICAL INVESTIGATIONS; THERMODYNAMIC DATA;

ACTIVATION ENERGY; CALCULATIONS; COPPER; LIGANDS; PHOSPHORUS COMPOUNDS; SELENIUM; SELENIUM COMPOUNDS; SULFUR; THERMODYNAMICS;

COPPER COMPOUNDS;

EID: 27744445874     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.19960020412     Document Type: Article

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26. 8] [3], which has the least distorted Cu-S cluster core. The differences in the Cu-Cu bond distances between the calculated and the experimental structures are very small for the Cu-S and the Cu-P bond lengths (0-4 pm) and bigger for most of the (nonbonding) Cu-Cu distances (3-22 pm). However, one should notice that Cu-Cu distances that are equivalent in 21 differ by up to 15 pm in the experimental structure. b) As with the ligand-free clusters, the range of Cu-E and Cu-Cu distances is bigger in the case of sulfur-containing compounds than for those containing selenium. Likewise one finds that through the substitution of sulfur for selenium, a significant decrease of Cu-E distances - 13 pm (in 15) to 8 pm (in 19) - is observed. However, in one case, there is almost no change (Cu3-S1 in 15). At 250.6 pm (251.4 pm), this metal-chalcogen bond is the longest found in these investigations. Also the metal-metal distances are for the most part shorter in the sulfur-containing clusters. The deviation of ± 5 pm compared with the copper selenide clusters is small, in fact there are bigger differences to be found in some cases when comparing with the "naked" clusters; the Cu-Cu contacts with a maximum of one sulfur bridge are particularly affected (e.g., 20: Cu2-Cu2′) as well as those which exhibit large metal-atom distances in both cluster types (e.g., 16: Cu2-Cu2′). The comparison of S-Cu-S angles with the corresponding Se-Cu-Se angles gives the same result as for the ligand-free clusters (except the S-Cu1-S′ angle in 19, +0.9°). The Cu-P bond lengths are up to 2 pm shorter in the sulfur-bridged clusters than in the selenium analogues. This might be put down to the slightly larger electronegativity of sulfur (2.58) [19] than selenium (2.55) [19] and therefore the associated somewhat stronger polarisation of the copper atoms.
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