Butterfly versus tetrahedral cluster structures for the unsaturated tetracobalt carbonyls Co4(CO)n (n = 10, 9): Major differences between cobalt and iridium

Lu Li; Xiuhui Zhang; Qian Shu Li; R. Bruce King

doi:10.1016/j.poly.2014.07.013

Butterfly versus tetrahedral cluster structures for the unsaturated tetracobalt carbonyls Co₄(CO)_n (n = 10, 9): Major differences between cobalt and iridium

Lu Li, Xiuhui Zhang^*, Qian Shu Li, R. Bruce King

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

The lowest energy structures of the unsaturated Co₄(CO) _n (n = 10, 9) clusters, potentially obtained by decarbonylation of the known Co₄(CO)₁₂, are predicted by density functional theory (DFT) to have central Co₄ butterflies with five bonding Co-Co interactions rather than Co₄ tetrahedra with six bonding Co-Co interactions. Both face-bridging μ₃-CO and edge-bridging μ-CO groups are found in such structures. Slightly higher energy Co ₄(CO)_n (n = 10, 9) butterfly structures are found with a unique μ₄-CO group bridging all four cobalt atoms similar to the lowest energy Co₄(CO)₁₁ structure from a previous DFT study. The lowest energy Co₄(CO)_n (n = 10, 9) structures differ significantly from their Ir₄(CO)_n analogues, which mainly have central Ir₄ tetrahedra rather than Ir₄ butterflies and only one or two edge-bridging μ-CO groups.

Original language	English
Pages (from-to)	628-633
Number of pages	6
Journal	Polyhedron
Volume	81
DOIs	https://doi.org/10.1016/j.poly.2014.07.013
Publication status	Published - 15 Oct 2014

Keywords

Butterfly clusters
Cobalt
Density functional theory
Metal carbonyls
Tetrahedral clusters

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10.1016/j.poly.2014.07.013

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title = "Butterfly versus tetrahedral cluster structures for the unsaturated tetracobalt carbonyls Co4(CO)n (n = 10, 9): Major differences between cobalt and iridium",

abstract = "The lowest energy structures of the unsaturated Co4(CO) n (n = 10, 9) clusters, potentially obtained by decarbonylation of the known Co4(CO)12, are predicted by density functional theory (DFT) to have central Co4 butterflies with five bonding Co-Co interactions rather than Co4 tetrahedra with six bonding Co-Co interactions. Both face-bridging μ3-CO and edge-bridging μ-CO groups are found in such structures. Slightly higher energy Co 4(CO)n (n = 10, 9) butterfly structures are found with a unique μ4-CO group bridging all four cobalt atoms similar to the lowest energy Co4(CO)11 structure from a previous DFT study. The lowest energy Co4(CO)n (n = 10, 9) structures differ significantly from their Ir4(CO)n analogues, which mainly have central Ir4 tetrahedra rather than Ir4 butterflies and only one or two edge-bridging μ-CO groups.",

keywords = "Butterfly clusters, Cobalt, Density functional theory, Metal carbonyls, Tetrahedral clusters",

author = "Lu Li and Xiuhui Zhang and Li, \{Qian Shu\} and King, \{R. Bruce\}",

year = "2014",

month = oct,

day = "15",

doi = "10.1016/j.poly.2014.07.013",

language = "English",

volume = "81",

pages = "628--633",

journal = "Polyhedron",

issn = "0277-5387",

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TY - JOUR

T1 - Butterfly versus tetrahedral cluster structures for the unsaturated tetracobalt carbonyls Co4(CO)n (n = 10, 9)

T2 - Major differences between cobalt and iridium

AU - Li, Lu

AU - Zhang, Xiuhui

AU - Li, Qian Shu

AU - King, R. Bruce

PY - 2014/10/15

Y1 - 2014/10/15

N2 - The lowest energy structures of the unsaturated Co4(CO) n (n = 10, 9) clusters, potentially obtained by decarbonylation of the known Co4(CO)12, are predicted by density functional theory (DFT) to have central Co4 butterflies with five bonding Co-Co interactions rather than Co4 tetrahedra with six bonding Co-Co interactions. Both face-bridging μ3-CO and edge-bridging μ-CO groups are found in such structures. Slightly higher energy Co 4(CO)n (n = 10, 9) butterfly structures are found with a unique μ4-CO group bridging all four cobalt atoms similar to the lowest energy Co4(CO)11 structure from a previous DFT study. The lowest energy Co4(CO)n (n = 10, 9) structures differ significantly from their Ir4(CO)n analogues, which mainly have central Ir4 tetrahedra rather than Ir4 butterflies and only one or two edge-bridging μ-CO groups.

AB - The lowest energy structures of the unsaturated Co4(CO) n (n = 10, 9) clusters, potentially obtained by decarbonylation of the known Co4(CO)12, are predicted by density functional theory (DFT) to have central Co4 butterflies with five bonding Co-Co interactions rather than Co4 tetrahedra with six bonding Co-Co interactions. Both face-bridging μ3-CO and edge-bridging μ-CO groups are found in such structures. Slightly higher energy Co 4(CO)n (n = 10, 9) butterfly structures are found with a unique μ4-CO group bridging all four cobalt atoms similar to the lowest energy Co4(CO)11 structure from a previous DFT study. The lowest energy Co4(CO)n (n = 10, 9) structures differ significantly from their Ir4(CO)n analogues, which mainly have central Ir4 tetrahedra rather than Ir4 butterflies and only one or two edge-bridging μ-CO groups.

KW - Butterfly clusters

KW - Cobalt

KW - Density functional theory

KW - Metal carbonyls

KW - Tetrahedral clusters

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U2 - 10.1016/j.poly.2014.07.013

DO - 10.1016/j.poly.2014.07.013

M3 - Article

AN - SCOPUS:84907328394

SN - 0277-5387

VL - 81

SP - 628

EP - 633

JO - Polyhedron

JF - Polyhedron

ER -

Butterfly versus tetrahedral cluster structures for the unsaturated tetracobalt carbonyls Co₄(CO)_n (n = 10, 9): Major differences between cobalt and iridium

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Keywords

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