Relative hemilabilities of H2B(az)2 (az = pyrazolyl, dimethylpyrazolyl, methimazolyl) chelates in the complexes [M(η-C3H5)(CO)2{H2B(az)2}] (M = Mo, W)

Robyn J. Abernethy; Mark R.St J. Foreman; Anthony F. Hill; Matthew K. Smith; Anthony C. Willis

doi:10.1039/c9dt03744f

Relative hemilabilities of H₂B(az)₂ (az = pyrazolyl, dimethylpyrazolyl, methimazolyl) chelates in the complexes [M(η-C₃H₅)(CO)₂{H₂B(az)₂}] (M = Mo, W)

Robyn J. Abernethy, Mark R.St J. Foreman, Anthony F. Hill^*, Matthew K. Smith, Anthony C. Willis

^*Corresponding author for this work

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Abstract

The reactions of [M(η³-C₃H₅)Br(CO)₂(NCMe)₂] (M = Mo, W) or [Mo(η³-C₃H₅)Br(CO)₂(PMe₂Ph)₂] with Na[H₂B(mt)₂] (mt = methimazolyl) affords the complexes [M(η³-C₃H₅)(CO)₂{κ³-H,S,S′-H₂B(mt)₂}], the 3-centre, 2-electron B-H-M interaction of which was found to be inert with respect to opening under mild conditions, while more forcing conditions (heating with PMe₂Ph) resulted in cleavage of the entire allyl and borate ligands to form [Mo(CO)₃(PMe₂Ph)₃]. In contrast, the reaction of [Mo(η³-C₃H₅)Br(CO)₂(NCMe)₂] with Na[H₂B(pz)₂] affords either [Mo(η³-C₃H₅)(CO)₂{κ³-H,N,N′-H₂B(pz)₂}] or (more likely) [Mo(η³-C₃H₅)(CO)₂(NCMe){κ²-N,N′-H₂B(pz)₂}] which in turn reacts with phosphines to provide [[Mo(η³-C₃H₅)(CO)₂(PPhR₂){κ²-N,N′-H₂B(pz)₂}] (R = Me, Ph). The reactions discussed indicate the propensity for 3-centre, 2-electron B-H-Mo interactions increases in the order H₂B(pz)₂ < H₂B(pz∗)₂ < H₂B(mt)₂ (pz∗ = 3,5-dimethypyrazolyl).

Original language	English
Pages (from-to)	781-796
Number of pages	16
Journal	Dalton Transactions
Volume	49
Issue number	3
DOIs	https://doi.org/10.1039/c9dt03744f
Publication status	Published - 2020

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@article{f8b4c5394f2f4074915b7fc42e48515c,

title = "Relative hemilabilities of H2B(az)2 (az = pyrazolyl, dimethylpyrazolyl, methimazolyl) chelates in the complexes [M(η-C3H5)(CO)2{H2B(az)2}] (M = Mo, W)",

abstract = "The reactions of [M(η3-C3H5)Br(CO)2(NCMe)2] (M = Mo, W) or [Mo(η3-C3H5)Br(CO)2(PMe2Ph)2] with Na[H2B(mt)2] (mt = methimazolyl) affords the complexes [M(η3-C3H5)(CO)2{κ3-H,S,S′-H2B(mt)2}], the 3-centre, 2-electron B-H-M interaction of which was found to be inert with respect to opening under mild conditions, while more forcing conditions (heating with PMe2Ph) resulted in cleavage of the entire allyl and borate ligands to form [Mo(CO)3(PMe2Ph)3]. In contrast, the reaction of [Mo(η3-C3H5)Br(CO)2(NCMe)2] with Na[H2B(pz)2] affords either [Mo(η3-C3H5)(CO)2{κ3-H,N,N′-H2B(pz)2}] or (more likely) [Mo(η3-C3H5)(CO)2(NCMe){κ2-N,N′-H2B(pz)2}] which in turn reacts with phosphines to provide [[Mo(η3-C3H5)(CO)2(PPhR2){κ2-N,N′-H2B(pz)2}] (R = Me, Ph). The reactions discussed indicate the propensity for 3-centre, 2-electron B-H-Mo interactions increases in the order H2B(pz)2 < H2B(pz∗)2 < H2B(mt)2 (pz∗ = 3,5-dimethypyrazolyl).",

author = "Abernethy, {Robyn J.} and Foreman, {Mark R.St J.} and Hill, {Anthony F.} and Smith, {Matthew K.} and Willis, {Anthony C.}",

note = "Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry.",

year = "2020",

doi = "10.1039/c9dt03744f",

language = "English",

volume = "49",

pages = "781--796",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "3",

}

TY - JOUR

T1 - Relative hemilabilities of H2B(az)2 (az = pyrazolyl, dimethylpyrazolyl, methimazolyl) chelates in the complexes [M(η-C3H5)(CO)2{H2B(az)2}] (M = Mo, W)

AU - Abernethy, Robyn J.

AU - Foreman, Mark R.St J.

AU - Hill, Anthony F.

AU - Smith, Matthew K.

AU - Willis, Anthony C.

PY - 2020

Y1 - 2020

N2 - The reactions of [M(η3-C3H5)Br(CO)2(NCMe)2] (M = Mo, W) or [Mo(η3-C3H5)Br(CO)2(PMe2Ph)2] with Na[H2B(mt)2] (mt = methimazolyl) affords the complexes [M(η3-C3H5)(CO)2{κ3-H,S,S′-H2B(mt)2}], the 3-centre, 2-electron B-H-M interaction of which was found to be inert with respect to opening under mild conditions, while more forcing conditions (heating with PMe2Ph) resulted in cleavage of the entire allyl and borate ligands to form [Mo(CO)3(PMe2Ph)3]. In contrast, the reaction of [Mo(η3-C3H5)Br(CO)2(NCMe)2] with Na[H2B(pz)2] affords either [Mo(η3-C3H5)(CO)2{κ3-H,N,N′-H2B(pz)2}] or (more likely) [Mo(η3-C3H5)(CO)2(NCMe){κ2-N,N′-H2B(pz)2}] which in turn reacts with phosphines to provide [[Mo(η3-C3H5)(CO)2(PPhR2){κ2-N,N′-H2B(pz)2}] (R = Me, Ph). The reactions discussed indicate the propensity for 3-centre, 2-electron B-H-Mo interactions increases in the order H2B(pz)2 < H2B(pz∗)2 < H2B(mt)2 (pz∗ = 3,5-dimethypyrazolyl).

AB - The reactions of [M(η3-C3H5)Br(CO)2(NCMe)2] (M = Mo, W) or [Mo(η3-C3H5)Br(CO)2(PMe2Ph)2] with Na[H2B(mt)2] (mt = methimazolyl) affords the complexes [M(η3-C3H5)(CO)2{κ3-H,S,S′-H2B(mt)2}], the 3-centre, 2-electron B-H-M interaction of which was found to be inert with respect to opening under mild conditions, while more forcing conditions (heating with PMe2Ph) resulted in cleavage of the entire allyl and borate ligands to form [Mo(CO)3(PMe2Ph)3]. In contrast, the reaction of [Mo(η3-C3H5)Br(CO)2(NCMe)2] with Na[H2B(pz)2] affords either [Mo(η3-C3H5)(CO)2{κ3-H,N,N′-H2B(pz)2}] or (more likely) [Mo(η3-C3H5)(CO)2(NCMe){κ2-N,N′-H2B(pz)2}] which in turn reacts with phosphines to provide [[Mo(η3-C3H5)(CO)2(PPhR2){κ2-N,N′-H2B(pz)2}] (R = Me, Ph). The reactions discussed indicate the propensity for 3-centre, 2-electron B-H-Mo interactions increases in the order H2B(pz)2 < H2B(pz∗)2 < H2B(mt)2 (pz∗ = 3,5-dimethypyrazolyl).

UR - http://www.scopus.com/inward/record.url?scp=85078348187&partnerID=8YFLogxK

U2 - 10.1039/c9dt03744f

DO - 10.1039/c9dt03744f

M3 - Article

SN - 1477-9226

VL - 49

SP - 781

EP - 796

JO - Dalton Transactions

JF - Dalton Transactions

IS - 3

ER -

Relative hemilabilities of H₂B(az)₂ (az = pyrazolyl, dimethylpyrazolyl, methimazolyl) chelates in the complexes [M(η-C₃H₅)(CO)₂{H₂B(az)₂}] (M = Mo, W)

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