Hydrogenating an organometallic carbon chain: buten-yn-diyl (CHCHCC) as a missing link

Michael J. Bartlett; Benjamin J. Frogley; Anthony F. Hill; Manab Sharma; Matthew K. Smith; Jas S. Ward

doi:10.1039/c9dt03229k

Hydrogenating an organometallic carbon chain: buten-yn-diyl (CHCHCC) as a missing link

Michael J. Bartlett, Benjamin J. Frogley, Anthony F. Hill, Manab Sharma, Matthew K. Smith, Jas S. Ward

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

5 Citations (Scopus)

Abstract

The sequential reaction of [Ru(CCCCH)Cl(CO)₂(PPh₃)₂] with [Ru(CO)₂(PPh₃)₃], and N-chlorosuccinimide affords the binuclear tetracarbido complex [Ru₂(μ-CCCC)Cl₂(CO)₄(PPh₃)₄]. This may be compared with the first example of a butenyndiyl bridged bimetallic complex [Ru₂(μ-CHCHCC)Cl₂(CO)₄(PPh₃)₄] which is obtained from the reaction of [Ru(CCCCH)Cl(CO)₂(PPh₃)₂] with [RuHCl(CO)(PPh₃)₃] followed by carbonylation. Characterisational data are discussed with reference to constituent model complexes [Ru(CCH)Cl(CO)₂(PPh₃)₂] and [Ru(CHCH₂)Cl(CO)₂(PPh₃)₂] in addition to DFT analysis of the bonding in the complexes [Ru₂(μ-L)Cl₂(CO)₄(PMe₃)₄] (L = CC-CC, CHCHCC, CHCH-CHCH). A range of other tetracarbido complexes which may be prepared from [RuCl(CCCCH)(CO)₂(PPh₃)₂] is also described and includes [RuAu(μ-C₄)Cl(CO)₃(PPh₃)₃], [RuIr(μ-C₄)Cl(CO)₃(PPh₃)₄], [RuIr(μ-C₄)H(NCMe)(CO)₃(PPh₃)₄]BF₄, [RuIr(μ-C₄)Cl(η²-O₂)(CO)₃(PPh₃)₄], [Ru₂Hg(μ-C₄)₂Cl₂(CO)₄(PPh₃)₄], [Ru₂Pt(μ-C₄)₂Cl₂(CO)₄(PPh₃)₆] and [Ru₂(μ-C₄)HCl(CO)₄(PPh₃)₄].

Original language	English
Pages (from-to)	16534-16554
Number of pages	21
Journal	Dalton Transactions
Volume	48
Issue number	44
DOIs	https://doi.org/10.1039/c9dt03229k
Publication status	Published - 2019
Externally published	Yes

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@article{9d57cca1542c424bb3524076b85a5d0a,

title = "Hydrogenating an organometallic carbon chain: buten-yn-diyl (CHCHCC) as a missing link",

abstract = "The sequential reaction of [Ru(CCCCH)Cl(CO)2(PPh3)2] with [Ru(CO)2(PPh3)3], and N-chlorosuccinimide affords the binuclear tetracarbido complex [Ru2(μ-CCCC)Cl2(CO)4(PPh3)4]. This may be compared with the first example of a butenyndiyl bridged bimetallic complex [Ru2(μ-CHCHCC)Cl2(CO)4(PPh3)4] which is obtained from the reaction of [Ru(CCCCH)Cl(CO)2(PPh3)2] with [RuHCl(CO)(PPh3)3] followed by carbonylation. Characterisational data are discussed with reference to constituent model complexes [Ru(CCH)Cl(CO)2(PPh3)2] and [Ru(CHCH2)Cl(CO)2(PPh3)2] in addition to DFT analysis of the bonding in the complexes [Ru2(μ-L)Cl2(CO)4(PMe3)4] (L = CC-CC, CHCHCC, CHCH-CHCH). A range of other tetracarbido complexes which may be prepared from [RuCl(CCCCH)(CO)2(PPh3)2] is also described and includes [RuAu(μ-C4)Cl(CO)3(PPh3)3], [RuIr(μ-C4)Cl(CO)3(PPh3)4], [RuIr(μ-C4)H(NCMe)(CO)3(PPh3)4]BF4, [RuIr(μ-C4)Cl(η2-O2)(CO)3(PPh3)4], [Ru2Hg(μ-C4)2Cl2(CO)4(PPh3)4], [Ru2Pt(μ-C4)2Cl2(CO)4(PPh3)6] and [Ru2(μ-C4)HCl(CO)4(PPh3)4].",

author = "Bartlett, {Michael J.} and Frogley, {Benjamin J.} and Hill, {Anthony F.} and Manab Sharma and Smith, {Matthew K.} and Ward, {Jas S.}",

note = "Funding Information: This work was supported by the Australian Research Council (DP170102695 and DP1901007231). The assistance of Dr Anthony C. Willis in the acquisition and interpretation of crystallographic data is gratefully acknowledged. This research was undertaken with the assistance of resources provided at the NCI National Facility systems at the Australian National University through the National Computational Merit Allocation Scheme supported by the Australian Government and the Tasmanian Partnership for Advanced Computing. Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9dt03229k",

language = "English",

volume = "48",

pages = "16534--16554",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "44",

}

TY - JOUR

T1 - Hydrogenating an organometallic carbon chain

T2 - buten-yn-diyl (CHCHCC) as a missing link

AU - Bartlett, Michael J.

AU - Frogley, Benjamin J.

AU - Hill, Anthony F.

AU - Sharma, Manab

AU - Smith, Matthew K.

AU - Ward, Jas S.

N1 - Funding Information: This work was supported by the Australian Research Council (DP170102695 and DP1901007231). The assistance of Dr Anthony C. Willis in the acquisition and interpretation of crystallographic data is gratefully acknowledged. This research was undertaken with the assistance of resources provided at the NCI National Facility systems at the Australian National University through the National Computational Merit Allocation Scheme supported by the Australian Government and the Tasmanian Partnership for Advanced Computing. Publisher Copyright: © 2019 The Royal Society of Chemistry.

PY - 2019

Y1 - 2019

N2 - The sequential reaction of [Ru(CCCCH)Cl(CO)2(PPh3)2] with [Ru(CO)2(PPh3)3], and N-chlorosuccinimide affords the binuclear tetracarbido complex [Ru2(μ-CCCC)Cl2(CO)4(PPh3)4]. This may be compared with the first example of a butenyndiyl bridged bimetallic complex [Ru2(μ-CHCHCC)Cl2(CO)4(PPh3)4] which is obtained from the reaction of [Ru(CCCCH)Cl(CO)2(PPh3)2] with [RuHCl(CO)(PPh3)3] followed by carbonylation. Characterisational data are discussed with reference to constituent model complexes [Ru(CCH)Cl(CO)2(PPh3)2] and [Ru(CHCH2)Cl(CO)2(PPh3)2] in addition to DFT analysis of the bonding in the complexes [Ru2(μ-L)Cl2(CO)4(PMe3)4] (L = CC-CC, CHCHCC, CHCH-CHCH). A range of other tetracarbido complexes which may be prepared from [RuCl(CCCCH)(CO)2(PPh3)2] is also described and includes [RuAu(μ-C4)Cl(CO)3(PPh3)3], [RuIr(μ-C4)Cl(CO)3(PPh3)4], [RuIr(μ-C4)H(NCMe)(CO)3(PPh3)4]BF4, [RuIr(μ-C4)Cl(η2-O2)(CO)3(PPh3)4], [Ru2Hg(μ-C4)2Cl2(CO)4(PPh3)4], [Ru2Pt(μ-C4)2Cl2(CO)4(PPh3)6] and [Ru2(μ-C4)HCl(CO)4(PPh3)4].

AB - The sequential reaction of [Ru(CCCCH)Cl(CO)2(PPh3)2] with [Ru(CO)2(PPh3)3], and N-chlorosuccinimide affords the binuclear tetracarbido complex [Ru2(μ-CCCC)Cl2(CO)4(PPh3)4]. This may be compared with the first example of a butenyndiyl bridged bimetallic complex [Ru2(μ-CHCHCC)Cl2(CO)4(PPh3)4] which is obtained from the reaction of [Ru(CCCCH)Cl(CO)2(PPh3)2] with [RuHCl(CO)(PPh3)3] followed by carbonylation. Characterisational data are discussed with reference to constituent model complexes [Ru(CCH)Cl(CO)2(PPh3)2] and [Ru(CHCH2)Cl(CO)2(PPh3)2] in addition to DFT analysis of the bonding in the complexes [Ru2(μ-L)Cl2(CO)4(PMe3)4] (L = CC-CC, CHCHCC, CHCH-CHCH). A range of other tetracarbido complexes which may be prepared from [RuCl(CCCCH)(CO)2(PPh3)2] is also described and includes [RuAu(μ-C4)Cl(CO)3(PPh3)3], [RuIr(μ-C4)Cl(CO)3(PPh3)4], [RuIr(μ-C4)H(NCMe)(CO)3(PPh3)4]BF4, [RuIr(μ-C4)Cl(η2-O2)(CO)3(PPh3)4], [Ru2Hg(μ-C4)2Cl2(CO)4(PPh3)4], [Ru2Pt(μ-C4)2Cl2(CO)4(PPh3)6] and [Ru2(μ-C4)HCl(CO)4(PPh3)4].

UR - http://www.scopus.com/inward/record.url?scp=85074875048&partnerID=8YFLogxK

U2 - 10.1039/c9dt03229k

DO - 10.1039/c9dt03229k

M3 - Article

C2 - 31576871

AN - SCOPUS:85074875048

SN - 1477-9226

VL - 48

SP - 16534

EP - 16554

JO - Dalton Transactions

JF - Dalton Transactions

IS - 44

ER -

Hydrogenating an organometallic carbon chain: buten-yn-diyl (CHCHCC) as a missing link

Abstract

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