Polyazolyl Chelate Chemistry. 6.1 Bidentate Coordination of HB(pz)3 (pz = Pyrazol-1-yl) to Ruthenium and Osmium:  Crystal Structure of [RuH(CO)(PPh3)2{κ2-HB(pz)3}]

Ian D. Burns; Anthony F. Hill; Andrew J.P. White; David J. Williams; James D.E.T. Wilton-Ely

doi:10.1021/om970991y

Polyazolyl Chelate Chemistry. 6.¹ Bidentate Coordination of HB(pz)₃ (pz = Pyrazol-1-yl) to Ruthenium and Osmium: Crystal Structure of [RuH(CO)(PPh₃)₂{κ²-HB(pz)₃}]

Ian D. Burns, Anthony F. Hill^*, Andrew J.P. White, David J. Williams, James D.E.T. Wilton-Ely

^*Corresponding author for this work

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Abstract

[RuHCl(CO)(PPh₃)₃], [Ru(SnPh₃)Cl(CO)(PPh₃)₂], or [RuH(CO)(NCMe)₂(PPh₃)₂]BF₄ reacts with K[HB(pz)₃] (pz = pyrazol-1-yl) to provide [RuH(CO)(PPh₃)₂{η²-HB(pz)₃}], thermolysis of which proceeds via loss of phosphine and formation of [RuH(CO)(PPh₃){η³-HB(pz)₃}]. The thiocarbonyl analogue [RuH(CS)(PPh₃)₂{η²-HB(pz)₃}] is obtained from [RuHCl(CS)(PPh₃)₃] and K[HB(pz)₃], thermolysis of which provides [RuH(CS)(PPh₃){η³-HB(pz)₃}]. In chloroform, this species provides [RuCl(CS)(PPh₃){η³-HB(pz)₃}]. [RuH(CS)(PPh₃)₂{η²-H₂B(bta) ₂}] (bta = benzotriazolyl) results from the reaction of [RuHCl(CS)(PPh₃)₃] with K[H₂B(bta)₂]. The hydride-bridged dinuclear complex [RuCu(μ-H)(CO)(PPh₃)₂{η³-HB(pz) ₃}]PF₆ results in high yield from the reaction of [RuH(CO)(PPh₃)₂{η²-HB(pz)₃}], with [Cu(NCMe)₄]BF₄. [Os(C₆H₅)-(CO)(PPh₃)₂{η ²-HB(pz)₃}] (from [Os(C₆H₅)Cl(CO)(PPh₃)₂] and K[HB(pz)₃]) converts on heating to [Os(C₆H₅)(CO)(PPh₃){η ³-HB(pz)3}].

Original language	English
Pages (from-to)	1552-1557
Number of pages	6
Journal	Organometallics
Volume	17
Issue number	8
Early online date	24 Mar 1998
DOIs	https://doi.org/10.1021/om970991y
Publication status	Published - Apr 1998
Externally published	Yes

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@article{1298affeb6774500b406d13877659b43,

title = "Polyazolyl Chelate Chemistry. 6.1 Bidentate Coordination of HB(pz)3 (pz = Pyrazol-1-yl) to Ruthenium and Osmium: Crystal Structure of [RuH(CO)(PPh3)2{κ2-HB(pz)3}]",

abstract = "[RuHCl(CO)(PPh3)3], [Ru(SnPh3)Cl(CO)(PPh3)2], or [RuH(CO)(NCMe)2(PPh3)2]BF4 reacts with K[HB(pz)3] (pz = pyrazol-1-yl) to provide [RuH(CO)(PPh3)2{η2-HB(pz)3}], thermolysis of which proceeds via loss of phosphine and formation of [RuH(CO)(PPh3){η3-HB(pz)3}]. The thiocarbonyl analogue [RuH(CS)(PPh3)2{η2-HB(pz)3}] is obtained from [RuHCl(CS)(PPh3)3] and K[HB(pz)3], thermolysis of which provides [RuH(CS)(PPh3){η3-HB(pz)3}]. In chloroform, this species provides [RuCl(CS)(PPh3){η3-HB(pz)3}]. [RuH(CS)(PPh3)2{η2-H2B(bta) 2}] (bta = benzotriazolyl) results from the reaction of [RuHCl(CS)(PPh3)3] with K[H2B(bta)2]. The hydride-bridged dinuclear complex [RuCu(μ-H)(CO)(PPh3)2{η3-HB(pz) 3}]PF6 results in high yield from the reaction of [RuH(CO)(PPh3)2{η2-HB(pz)3}], with [Cu(NCMe)4]BF4. [Os(C6H5)-(CO)(PPh3)2{η 2-HB(pz)3}] (from [Os(C6H5)Cl(CO)(PPh3)2] and K[HB(pz)3]) converts on heating to [Os(C6H5)(CO)(PPh3){η 3-HB(pz)3}].",

keywords = "Pi-acceptor ligands, Molecular-structure, Stannyl complexes, Rhodium complex, Reactivity, Ruthenatetraboranes, Derivatives, Activation, Versatile",

author = "Burns, {Ian D.} and Hill, {Anthony F.} and White, {Andrew J.P.} and Williams, {David J.} and Wilton-Ely, {James D.E.T.}",

year = "1998",

month = apr,

doi = "10.1021/om970991y",

language = "English",

volume = "17",

pages = "1552--1557",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Polyazolyl Chelate Chemistry. 6.1 Bidentate Coordination of HB(pz)3 (pz = Pyrazol-1-yl) to Ruthenium and Osmium: Crystal Structure of [RuH(CO)(PPh3)2{κ2-HB(pz)3}]

AU - Burns, Ian D.

AU - Hill, Anthony F.

AU - White, Andrew J.P.

AU - Williams, David J.

AU - Wilton-Ely, James D.E.T.

PY - 1998/4

Y1 - 1998/4

N2 - [RuHCl(CO)(PPh3)3], [Ru(SnPh3)Cl(CO)(PPh3)2], or [RuH(CO)(NCMe)2(PPh3)2]BF4 reacts with K[HB(pz)3] (pz = pyrazol-1-yl) to provide [RuH(CO)(PPh3)2{η2-HB(pz)3}], thermolysis of which proceeds via loss of phosphine and formation of [RuH(CO)(PPh3){η3-HB(pz)3}]. The thiocarbonyl analogue [RuH(CS)(PPh3)2{η2-HB(pz)3}] is obtained from [RuHCl(CS)(PPh3)3] and K[HB(pz)3], thermolysis of which provides [RuH(CS)(PPh3){η3-HB(pz)3}]. In chloroform, this species provides [RuCl(CS)(PPh3){η3-HB(pz)3}]. [RuH(CS)(PPh3)2{η2-H2B(bta) 2}] (bta = benzotriazolyl) results from the reaction of [RuHCl(CS)(PPh3)3] with K[H2B(bta)2]. The hydride-bridged dinuclear complex [RuCu(μ-H)(CO)(PPh3)2{η3-HB(pz) 3}]PF6 results in high yield from the reaction of [RuH(CO)(PPh3)2{η2-HB(pz)3}], with [Cu(NCMe)4]BF4. [Os(C6H5)-(CO)(PPh3)2{η 2-HB(pz)3}] (from [Os(C6H5)Cl(CO)(PPh3)2] and K[HB(pz)3]) converts on heating to [Os(C6H5)(CO)(PPh3){η 3-HB(pz)3}].

AB - [RuHCl(CO)(PPh3)3], [Ru(SnPh3)Cl(CO)(PPh3)2], or [RuH(CO)(NCMe)2(PPh3)2]BF4 reacts with K[HB(pz)3] (pz = pyrazol-1-yl) to provide [RuH(CO)(PPh3)2{η2-HB(pz)3}], thermolysis of which proceeds via loss of phosphine and formation of [RuH(CO)(PPh3){η3-HB(pz)3}]. The thiocarbonyl analogue [RuH(CS)(PPh3)2{η2-HB(pz)3}] is obtained from [RuHCl(CS)(PPh3)3] and K[HB(pz)3], thermolysis of which provides [RuH(CS)(PPh3){η3-HB(pz)3}]. In chloroform, this species provides [RuCl(CS)(PPh3){η3-HB(pz)3}]. [RuH(CS)(PPh3)2{η2-H2B(bta) 2}] (bta = benzotriazolyl) results from the reaction of [RuHCl(CS)(PPh3)3] with K[H2B(bta)2]. The hydride-bridged dinuclear complex [RuCu(μ-H)(CO)(PPh3)2{η3-HB(pz) 3}]PF6 results in high yield from the reaction of [RuH(CO)(PPh3)2{η2-HB(pz)3}], with [Cu(NCMe)4]BF4. [Os(C6H5)-(CO)(PPh3)2{η 2-HB(pz)3}] (from [Os(C6H5)Cl(CO)(PPh3)2] and K[HB(pz)3]) converts on heating to [Os(C6H5)(CO)(PPh3){η 3-HB(pz)3}].

KW - Pi-acceptor ligands

KW - Molecular-structure

KW - Stannyl complexes

KW - Rhodium complex

KW - Reactivity

KW - Ruthenatetraboranes

KW - Derivatives

KW - Activation

KW - Versatile

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U2 - 10.1021/om970991y

DO - 10.1021/om970991y

M3 - Article

SN - 0276-7333

VL - 17

SP - 1552

EP - 1557

JO - Organometallics

JF - Organometallics

IS - 8

ER -

Polyazolyl Chelate Chemistry. 6.¹ Bidentate Coordination of HB(pz)₃ (pz = Pyrazol-1-yl) to Ruthenium and Osmium: Crystal Structure of [RuH(CO)(PPh₃)₂{κ²-HB(pz)₃}]

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