Boron functionalization of bis(pyrazolyl)borate ligands: Molecular structures of [RuX(PPh3)2{(MeO)2B(Pz) 2}] (X = H, Cl; pz = pyrazol-1-yl)

Robyn J. Abernethy; Anthony F. Hill; Matthew K. Smith; Anthony C. Willis

doi:10.1021/om9006592

Boron functionalization of bis(pyrazolyl)borate ligands: Molecular structures of [RuX(PPh₃)₂{(MeO)₂B(Pz) ₂}] (X = H, Cl; pz = pyrazol-1-yl)

Robyn J. Abernethy
, Anthony F. Hill
, Matthew K. Smith
, Anthony C. Willis

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

20 Citations (Scopus)

Abstract

The reaction of [RuCl₂(PPh₃)₃] with K[H₂B(pz)₂] (pz = pyrazol-1-yl) in tetrahydrofuran at room temperature provides the known hydro/ns(pyrazolyl)borate complex [RuH(PPh ₃)₂{HB(pz)₃}] (1b) via pyrazole scrambling. In contrast, the reaction of [RuCl₂(PPh₃)₃] with K[H₂B(pz)₂] in methanol does not, as previously reported, provide [Ru(PPh₃)₂{H₂B(pz)₂} ₂] but, rather, a mixture of the complexes [RuX(PPh₃) ₂{κ³O,N,N′-(MeO)₂B(pz) ₂}] (X = H (2a), Cl (2b)) and ttt-[RuCl₂(HpZ) ₂-(PPh₃)₂] (3), each of which have been structurally characterized. Although the resulting bulk admixtures of 2a,b have so far proved inseparable, treatment with mercuric chloride cleanly converts the 2a component to 2b. Heating 2b with 1,2-bis(dicyclohexylphosphino)ethane (dcpe) results in substitution of both phosphine ligands and the formation of [RuCl(dcpe){κ³O,N,N′-(MeO)₂B(pz)₂}] (4) in which the ruthenium-ether linkage is ultimately retained.

Original language	English
Pages (from-to)	6152-6159
Number of pages	8
Journal	Organometallics
Volume	28
Issue number	21
DOIs	https://doi.org/10.1021/om9006592
Publication status	Published - 9 Nov 2009

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@article{772f4f4208974c9a80ca3f7ffd4afd94,

title = "Boron functionalization of bis(pyrazolyl)borate ligands: Molecular structures of [RuX(PPh3)2\{(MeO)2B(Pz) 2\}] (X = H, Cl; pz = pyrazol-1-yl)",

abstract = "The reaction of [RuCl2(PPh3)3] with K[H2B(pz)2] (pz = pyrazol-1-yl) in tetrahydrofuran at room temperature provides the known hydro/ns(pyrazolyl)borate complex [RuH(PPh 3)2\{HB(pz)3\}] (1b) via pyrazole scrambling. In contrast, the reaction of [RuCl2(PPh3)3] with K[H2B(pz)2] in methanol does not, as previously reported, provide [Ru(PPh3)2\{H2B(pz)2\} 2] but, rather, a mixture of the complexes [RuX(PPh3) 2\{κ3O,N,N′-(MeO)2B(pz) 2\}] (X = H (2a), Cl (2b)) and ttt-[RuCl2(HpZ) 2-(PPh3)2] (3), each of which have been structurally characterized. Although the resulting bulk admixtures of 2a,b have so far proved inseparable, treatment with mercuric chloride cleanly converts the 2a component to 2b. Heating 2b with 1,2-bis(dicyclohexylphosphino)ethane (dcpe) results in substitution of both phosphine ligands and the formation of [RuCl(dcpe)\{κ3O,N,N′-(MeO)2B(pz)2\}] (4) in which the ruthenium-ether linkage is ultimately retained.",

author = "Abernethy, \{Robyn J.\} and Hill, \{Anthony F.\} and Smith, \{Matthew K.\} and Willis, \{Anthony C.\}",

year = "2009",

month = nov,

day = "9",

doi = "10.1021/om9006592",

language = "English",

volume = "28",

pages = "6152--6159",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "21",

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TY - JOUR

T1 - Boron functionalization of bis(pyrazolyl)borate ligands

T2 - Molecular structures of [RuX(PPh3)2{(MeO)2B(Pz) 2}] (X = H, Cl; pz = pyrazol-1-yl)

AU - Abernethy, Robyn J.

AU - Hill, Anthony F.

AU - Smith, Matthew K.

AU - Willis, Anthony C.

PY - 2009/11/9

Y1 - 2009/11/9

N2 - The reaction of [RuCl2(PPh3)3] with K[H2B(pz)2] (pz = pyrazol-1-yl) in tetrahydrofuran at room temperature provides the known hydro/ns(pyrazolyl)borate complex [RuH(PPh 3)2{HB(pz)3}] (1b) via pyrazole scrambling. In contrast, the reaction of [RuCl2(PPh3)3] with K[H2B(pz)2] in methanol does not, as previously reported, provide [Ru(PPh3)2{H2B(pz)2} 2] but, rather, a mixture of the complexes [RuX(PPh3) 2{κ3O,N,N′-(MeO)2B(pz) 2}] (X = H (2a), Cl (2b)) and ttt-[RuCl2(HpZ) 2-(PPh3)2] (3), each of which have been structurally characterized. Although the resulting bulk admixtures of 2a,b have so far proved inseparable, treatment with mercuric chloride cleanly converts the 2a component to 2b. Heating 2b with 1,2-bis(dicyclohexylphosphino)ethane (dcpe) results in substitution of both phosphine ligands and the formation of [RuCl(dcpe){κ3O,N,N′-(MeO)2B(pz)2}] (4) in which the ruthenium-ether linkage is ultimately retained.

AB - The reaction of [RuCl2(PPh3)3] with K[H2B(pz)2] (pz = pyrazol-1-yl) in tetrahydrofuran at room temperature provides the known hydro/ns(pyrazolyl)borate complex [RuH(PPh 3)2{HB(pz)3}] (1b) via pyrazole scrambling. In contrast, the reaction of [RuCl2(PPh3)3] with K[H2B(pz)2] in methanol does not, as previously reported, provide [Ru(PPh3)2{H2B(pz)2} 2] but, rather, a mixture of the complexes [RuX(PPh3) 2{κ3O,N,N′-(MeO)2B(pz) 2}] (X = H (2a), Cl (2b)) and ttt-[RuCl2(HpZ) 2-(PPh3)2] (3), each of which have been structurally characterized. Although the resulting bulk admixtures of 2a,b have so far proved inseparable, treatment with mercuric chloride cleanly converts the 2a component to 2b. Heating 2b with 1,2-bis(dicyclohexylphosphino)ethane (dcpe) results in substitution of both phosphine ligands and the formation of [RuCl(dcpe){κ3O,N,N′-(MeO)2B(pz)2}] (4) in which the ruthenium-ether linkage is ultimately retained.

UR - https://www.scopus.com/pages/publications/70350707646

U2 - 10.1021/om9006592

DO - 10.1021/om9006592

M3 - Article

SN - 0276-7333

VL - 28

SP - 6152

EP - 6159

JO - Organometallics

JF - Organometallics

IS - 21

ER -

Boron functionalization of bis(pyrazolyl)borate ligands: Molecular structures of [RuX(PPh₃)₂{(MeO)₂B(Pz) ₂}] (X = H, Cl; pz = pyrazol-1-yl)

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