Syntheses and structures of tetranuclear cluster complexes of molybdenum [Mo4(μ3-S)2(μ2-S) 4X2-(PMe3)6] (X= SH, Cl, Br, I, SCN) and [Mo4(μ3-S)2-(μ2-S) 4(dtc)2(PMe3)4] (dtc = diethyldithiocarbamate)

Kiyoshi Tsuge

doi:10.1007/BF01171191

Syntheses and structures of tetranuclear cluster complexes of molybdenum [Mo₄(μ₃-S)₂(μ₂-S) ₄X₂-(PMe₃)₆] (X= SH, Cl, Br, I, SCN) and [Mo₄(μ₃-S)₂-(μ₂-S) ₄(dtc)₂(PMe₃)₄] (dtc = diethyldithiocarbamate)

Kiyoshi Tsuge^*

^*Corresponding author for this work

Department of Chemistry

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

15 Scopus citations

Abstract

A molybdenum cluster complex [Mo₄(μ₃-S)₂(μ₂-S) ₄(SH)₂(PMe₃)₆] has been synthesized by the reaction of (NH₄)₂Mo₃S₁₃ with trimethylphosphine. The cluster core is composed of lour molybdenum atoms arranged in the rhombus bridged by two capping and four bridging sulfur atoms. Two SH and six trimethylphosphinc ligands are coordinated to the terminal positions. The mean oxidation states of molybdenum is +3.5 and there are five Mo-Mo bonds consistent with ten metal cluster electrons. The complex has been converted into [Mo₄(μ₃-S)₂(μ₂-S) ₄X₂(PMe₃)₆] (X = Cl, Br, I, SCN) and [Mo₄(μ₃-S)₂(μ₂ ₂-S)₄ (dtc)₂(PMe₃)₄] (dtc = diethyldithiocarbamate). In the case of the dtc complex, two terminal trimethylphosphine ligands are displaced and dtc ligands are coordinated in chelate fashion. The structures of the SH, Cl, Br, and dtc complexes have been determined by X-ray crystallography. Molecular orbital calculations with DV-Xα method has shown large HOMO-LUMO gaps (1.52-1.74eV) for [Mo₄S₆X₂(PH₃)₄] (X = SH, Cl, and Br).

Original language	English
Pages (from-to)	407-421
Number of pages	15
Journal	Journal of Cluster Science
Volume	7
Issue number	3
DOIs	https://doi.org/10.1007/BF01171191
State	Published - 1996

Keywords

Diethyldithiocarbamate
Molybdenum
Sulfide
Tetranuclear cluster
Trimethylphosphine

ASJC Scopus subject areas

Biochemistry
General Chemistry
General Materials Science
Condensed Matter Physics

Access to Document

10.1007/BF01171191

Cite this

@article{19d9d38576184d1d8fecdf18dc92d670,

title = "Syntheses and structures of tetranuclear cluster complexes of molybdenum [Mo4(μ3-S)2(μ2-S) 4X2-(PMe3)6] (X= SH, Cl, Br, I, SCN) and [Mo4(μ3-S)2-(μ2-S) 4(dtc)2(PMe3)4] (dtc = diethyldithiocarbamate)",

abstract = "A molybdenum cluster complex [Mo4(μ3-S)2(μ2-S) 4(SH)2(PMe3)6] has been synthesized by the reaction of (NH4)2Mo3S13 with trimethylphosphine. The cluster core is composed of lour molybdenum atoms arranged in the rhombus bridged by two capping and four bridging sulfur atoms. Two SH and six trimethylphosphinc ligands are coordinated to the terminal positions. The mean oxidation states of molybdenum is +3.5 and there are five Mo-Mo bonds consistent with ten metal cluster electrons. The complex has been converted into [Mo4(μ3-S)2(μ2-S) 4X2(PMe3)6] (X = Cl, Br, I, SCN) and [Mo4(μ3-S)2(μ2 2-S)4 (dtc)2(PMe3)4] (dtc = diethyldithiocarbamate). In the case of the dtc complex, two terminal trimethylphosphine ligands are displaced and dtc ligands are coordinated in chelate fashion. The structures of the SH, Cl, Br, and dtc complexes have been determined by X-ray crystallography. Molecular orbital calculations with DV-Xα method has shown large HOMO-LUMO gaps (1.52-1.74eV) for [Mo4S6X2(PH3)4] (X = SH, Cl, and Br).",

keywords = "Diethyldithiocarbamate, Molybdenum, Sulfide, Tetranuclear cluster, Trimethylphosphine",

author = "Kiyoshi Tsuge",

year = "1996",

doi = "10.1007/BF01171191",

language = "英語",

volume = "7",

pages = "407--421",

journal = "Journal of Cluster Science",

issn = "1040-7278",

publisher = "Springer New York",

number = "3",

}

TY - JOUR

T1 - Syntheses and structures of tetranuclear cluster complexes of molybdenum [Mo4(μ3-S)2(μ2-S) 4X2-(PMe3)6] (X= SH, Cl, Br, I, SCN) and [Mo4(μ3-S)2-(μ2-S) 4(dtc)2(PMe3)4] (dtc = diethyldithiocarbamate)

AU - Tsuge, Kiyoshi

PY - 1996

Y1 - 1996

N2 - A molybdenum cluster complex [Mo4(μ3-S)2(μ2-S) 4(SH)2(PMe3)6] has been synthesized by the reaction of (NH4)2Mo3S13 with trimethylphosphine. The cluster core is composed of lour molybdenum atoms arranged in the rhombus bridged by two capping and four bridging sulfur atoms. Two SH and six trimethylphosphinc ligands are coordinated to the terminal positions. The mean oxidation states of molybdenum is +3.5 and there are five Mo-Mo bonds consistent with ten metal cluster electrons. The complex has been converted into [Mo4(μ3-S)2(μ2-S) 4X2(PMe3)6] (X = Cl, Br, I, SCN) and [Mo4(μ3-S)2(μ2 2-S)4 (dtc)2(PMe3)4] (dtc = diethyldithiocarbamate). In the case of the dtc complex, two terminal trimethylphosphine ligands are displaced and dtc ligands are coordinated in chelate fashion. The structures of the SH, Cl, Br, and dtc complexes have been determined by X-ray crystallography. Molecular orbital calculations with DV-Xα method has shown large HOMO-LUMO gaps (1.52-1.74eV) for [Mo4S6X2(PH3)4] (X = SH, Cl, and Br).

AB - A molybdenum cluster complex [Mo4(μ3-S)2(μ2-S) 4(SH)2(PMe3)6] has been synthesized by the reaction of (NH4)2Mo3S13 with trimethylphosphine. The cluster core is composed of lour molybdenum atoms arranged in the rhombus bridged by two capping and four bridging sulfur atoms. Two SH and six trimethylphosphinc ligands are coordinated to the terminal positions. The mean oxidation states of molybdenum is +3.5 and there are five Mo-Mo bonds consistent with ten metal cluster electrons. The complex has been converted into [Mo4(μ3-S)2(μ2-S) 4X2(PMe3)6] (X = Cl, Br, I, SCN) and [Mo4(μ3-S)2(μ2 2-S)4 (dtc)2(PMe3)4] (dtc = diethyldithiocarbamate). In the case of the dtc complex, two terminal trimethylphosphine ligands are displaced and dtc ligands are coordinated in chelate fashion. The structures of the SH, Cl, Br, and dtc complexes have been determined by X-ray crystallography. Molecular orbital calculations with DV-Xα method has shown large HOMO-LUMO gaps (1.52-1.74eV) for [Mo4S6X2(PH3)4] (X = SH, Cl, and Br).

KW - Diethyldithiocarbamate

KW - Molybdenum

KW - Sulfide

KW - Tetranuclear cluster

KW - Trimethylphosphine

UR - http://www.scopus.com/inward/record.url?scp=0001783364&partnerID=8YFLogxK

U2 - 10.1007/BF01171191

DO - 10.1007/BF01171191

M3 - 学術論文

AN - SCOPUS:0001783364

SN - 1040-7278

VL - 7

SP - 407

EP - 421

JO - Journal of Cluster Science

JF - Journal of Cluster Science

IS - 3

ER -