A new family of flexible scorpionate ligands based on 2-mercaptopyridine

Gavin Dyson; Alex Hamilton; Byron Mitchell; Gareth R. Owen

doi:10.1039/b905409j

A new family of flexible scorpionate ligands based on 2-mercaptopyridine

Gavin Dyson, Alex Hamilton, Byron Mitchell, Gareth R. Owen

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

36 Citations (Scopus)

Abstract

A new family of flexible scorpionate ligands based on 2-mercaptopyridine is reported. The tris- and bis-substituted ligands, K[HB(mp)₃] (1) and Na[H₂B(mp)₂] (2) (mp = 2-mercaptopyridine) have been prepared and fully characterised. The structural characterisation of 1 reveals an unprecedented μ₃-κ³-SS′H- η¹η¹η²-κ²- S″C-η¹η¹-κ¹-S′- η¹ coordination mode. The coordination of both 1 and 2 to copper(i) complexes containing triphenylphosphine and tricyclohexylphosphine co-ligands is investigated suggesting κ³-SSS coordination modes for [Cu{HB(mp)₃}(PR₃)] {where R = Ph (3); R = Cy, (4)} and κ³-SSH coordination modes for [Cu{H₂B(mp) ₂}(PR₃)] {where R = Ph (5); R = Cy (6)} the latter confirmed by structural characterisation of 5. A structural comparison with the sulfur based scorpionates, HB(mt)₃ and H₂B(mt)₂ (mt = methyl-2-mercaptoimidazole) is made in terms of the degree of tautomerisation of the heterocyclic rings.

Original language	English
Pages (from-to)	6120-6126
Number of pages	7
Journal	Dalton Transactions
Issue number	31
DOIs	https://doi.org/10.1039/b905409j
Publication status	Published - 10 Aug 2009
Externally published	Yes

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title = "A new family of flexible scorpionate ligands based on 2-mercaptopyridine",

abstract = "A new family of flexible scorpionate ligands based on 2-mercaptopyridine is reported. The tris- and bis-substituted ligands, K[HB(mp)3] (1) and Na[H2B(mp)2] (2) (mp = 2-mercaptopyridine) have been prepared and fully characterised. The structural characterisation of 1 reveals an unprecedented μ3-κ3-SS′H- η1η1η2-κ2- S″C-η1η1-κ1-S′- η1 coordination mode. The coordination of both 1 and 2 to copper(i) complexes containing triphenylphosphine and tricyclohexylphosphine co-ligands is investigated suggesting κ3-SSS coordination modes for [Cu{HB(mp)3}(PR3)] {where R = Ph (3); R = Cy, (4)} and κ3-SSH coordination modes for [Cu{H2B(mp) 2}(PR3)] {where R = Ph (5); R = Cy (6)} the latter confirmed by structural characterisation of 5. A structural comparison with the sulfur based scorpionates, HB(mt)3 and H2B(mt)2 (mt = methyl-2-mercaptoimidazole) is made in terms of the degree of tautomerisation of the heterocyclic rings.",

author = "Gavin Dyson and Alex Hamilton and Byron Mitchell and Owen, {Gareth R.}",

year = "2009",

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doi = "10.1039/b905409j",

language = "English",

pages = "6120--6126",

journal = "Dalton Transactions",

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publisher = "Royal Society of Chemistry",

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T1 - A new family of flexible scorpionate ligands based on 2-mercaptopyridine

AU - Dyson, Gavin

AU - Hamilton, Alex

AU - Mitchell, Byron

AU - Owen, Gareth R.

PY - 2009/8/10

Y1 - 2009/8/10

N2 - A new family of flexible scorpionate ligands based on 2-mercaptopyridine is reported. The tris- and bis-substituted ligands, K[HB(mp)3] (1) and Na[H2B(mp)2] (2) (mp = 2-mercaptopyridine) have been prepared and fully characterised. The structural characterisation of 1 reveals an unprecedented μ3-κ3-SS′H- η1η1η2-κ2- S″C-η1η1-κ1-S′- η1 coordination mode. The coordination of both 1 and 2 to copper(i) complexes containing triphenylphosphine and tricyclohexylphosphine co-ligands is investigated suggesting κ3-SSS coordination modes for [Cu{HB(mp)3}(PR3)] {where R = Ph (3); R = Cy, (4)} and κ3-SSH coordination modes for [Cu{H2B(mp) 2}(PR3)] {where R = Ph (5); R = Cy (6)} the latter confirmed by structural characterisation of 5. A structural comparison with the sulfur based scorpionates, HB(mt)3 and H2B(mt)2 (mt = methyl-2-mercaptoimidazole) is made in terms of the degree of tautomerisation of the heterocyclic rings.

AB - A new family of flexible scorpionate ligands based on 2-mercaptopyridine is reported. The tris- and bis-substituted ligands, K[HB(mp)3] (1) and Na[H2B(mp)2] (2) (mp = 2-mercaptopyridine) have been prepared and fully characterised. The structural characterisation of 1 reveals an unprecedented μ3-κ3-SS′H- η1η1η2-κ2- S″C-η1η1-κ1-S′- η1 coordination mode. The coordination of both 1 and 2 to copper(i) complexes containing triphenylphosphine and tricyclohexylphosphine co-ligands is investigated suggesting κ3-SSS coordination modes for [Cu{HB(mp)3}(PR3)] {where R = Ph (3); R = Cy, (4)} and κ3-SSH coordination modes for [Cu{H2B(mp) 2}(PR3)] {where R = Ph (5); R = Cy (6)} the latter confirmed by structural characterisation of 5. A structural comparison with the sulfur based scorpionates, HB(mt)3 and H2B(mt)2 (mt = methyl-2-mercaptoimidazole) is made in terms of the degree of tautomerisation of the heterocyclic rings.

U2 - 10.1039/b905409j

DO - 10.1039/b905409j

M3 - Article

C2 - 20449107

AN - SCOPUS:68149142642

SN - 1477-9226

SP - 6120

EP - 6126

JO - Dalton Transactions

JF - Dalton Transactions

IS - 31

ER -

A new family of flexible scorpionate ligands based on 2-mercaptopyridine

Abstract

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