Boron-boron bond oxidative addition to rhodium(I) and iridium(I) centres

William Clegg; Fiona J. Lawlor; Todd B. Marder; Paul Nguyen; Nicholas C. Norman; A. Guy Orpen; Michael J. Quayle; Craig R. Rice; Edward G. Robins; Andrew J. Scott; Fabio E.S. Souza; Graham Stringer; George R. Whittell

doi:10.1039/A705374F

Boron-boron bond oxidative addition to rhodium(I) and iridium(I) centres

William Clegg, Fiona J. Lawlor, Todd B. Marder, Paul Nguyen, Nicholas C. Norman, A. Guy Orpen, Michael J. Quayle, Craig R. Rice, Edward G. Robins, Andrew J. Scott, Fabio E.S. Souza, Graham Stringer, George R. Whittell

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

51 Citations (Scopus)

Abstract

The reaction between the diborane(4) compound B₂(1,2-O₂C₆H₄)₂ and either of the rhodium(I) complexes [RhCl(PPh₃)₃] or [{Rh(μ-Cl)(PPh₃)₂}₂] afforded the colourless rhodium(III) bis(boryl) species [RhCl(PPh₃)₂-{B(1,2-O₂C₆H ₄)}₂]. Similar reactions have been carried out with the diborane(4) compounds B₂(1,2-O₂-4-Bu^tC₆H₃) ₂, B₂(1,2-O₂-3,5-Bu^t ₂C ₆H₂)₂, B₂(1,2-O₂-3-MeC₆H₃)₂, B₂(1,2-O₂-4-MeC₆H₃)₂, B₂(1,2-O₂-3-MeOC₆H₃)₂, B₂(1,2-S₂C₆H₄)₂, B₂(1,2-S₂-4-MeC₆H₃)₂ and B₂[R,R-1,2-O₂CH(CO₂Me)CH(CO ₂Me)]₂ affording analogous rhodium complexes all of which have been characterised spectroscopically. The complexes derived from the reactions with B₂(1,2-O₂C₆H₄)₂ and B₂(1,2-O₂-3-MeC₆H₃)₂ have also been characterised by X-ray crystallography, the structures comprising a five-co-ordinate rhodium centre with a square-based-pyramidal geometry in which the apical site is occupied by a boryl group and the phosphines are mutually trims in basal positions. Reactivity studies have also been carried out for [RhCl(PPh₃)₂{B(1,2-O₂C₆H ₄)}₂]. Hydrolysis or alcoholysis with catechol afforded [RhH₂Cl(PPh₃)₃] and either B₂(1,2-O₂C₆H₄)₂(μ-O) or B₂(1,2-O₂C₆H₄)₃ and addition of the phosphines PMe₃, PEt₃ and PMe₂Ph afforded the new bis(boryl) compounds cis,mer-[RhCl(PMe₃)₃{B(1,2-O₂C ₆H₄)}₂], [RhCl(PEt₃)₂-{B(1,2-O₂C₆H ₄)}₂] and cis,mer-[RhCl(PMe₂Ph)₃{B(1,2-O₂C ₆H₄)}₂], the PEt₃ complex having been characterised by X-ray crystallography and shown to be similar to the PPh₃ complex. The iridium analogue [IrCl(PEt₃)₂-{B(1,2-O₂C₆H ₄)}₂] was also prepared from the reaction between [IrCl(PEt₃)₃] and B₂(1,2-O₂C₆H₄)₂ and shown by X-ray crystallography to be isomorphous with the rhodium complex. Reactions between [RhCl(PPh₃)₂-{B(1,2-O₂C₆H ₄)}₂] and the phosphines PPrⁱ ₃, P(C₆H₁₁)₃, 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) are also described although these do not result in new rhodium boryl complexes. The reaction between [{RhCl(dppe)}₂] and B₂(1,2-O₂C₆H₄)₂ afforded a compound tentatively assigned as [Rh(dppe)₂{B(1,2-O₂C₆H₄)}] with analogous compounds being formed with the diborane(4) compounds B₂(1,2-O₂-3-MeC₆H₃)₂ and B₂(1,2-O₂-4-MeC₆H₃)₂. Finally, the reaction between [Rh(PMe₃)₄]Cl and the diborane(4) compound B₂(1,2-O₂C₆H₄)₂ is described which affords cis,mer-[RhCl(PMe₃)₃{B(1,2-O₂C ₆H₄)}₂]. Analogous reactions with B₂(1,2-O₂-3,5-Bu^t ₂C ₆H₂)₂, B₂(1,2-O₂-3-MeC₆H₃)₂ and B₂[R,R-1,2-O₂CH(CO₂Me)CH-(CO ₂MeJ]₂ afforded similar products.

Original language	English
Pages (from-to)	301-309
Number of pages	9
Journal	Journal of the Chemical Society - Dalton Transactions
Issue number	2
DOIs	https://doi.org/10.1039/A705374F
Publication status	Published - 21 Jan 1998
Externally published	Yes

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Clegg, W., Lawlor, F. J., Marder, T. B., Nguyen, P., Norman, N. C., Orpen, A. G., Quayle, M. J., Rice, C. R., Robins, E. G., Scott, A. J., Souza, F. E. S., Stringer, G., & Whittell, G. R. (1998). Boron-boron bond oxidative addition to rhodium(I) and iridium(I) centres. Journal of the Chemical Society - Dalton Transactions, (2), 301-309. https://doi.org/10.1039/A705374F

@article{828e93f476a248d294f3812b36ffd3d0,

title = "Boron-boron bond oxidative addition to rhodium(I) and iridium(I) centres",

abstract = "The reaction between the diborane(4) compound B2(1,2-O2C6H4)2 and either of the rhodium(I) complexes [RhCl(PPh3)3] or [\{Rh(μ-Cl)(PPh3)2\}2] afforded the colourless rhodium(III) bis(boryl) species [RhCl(PPh3)2-\{B(1,2-O2C6H 4)\}2]. Similar reactions have been carried out with the diborane(4) compounds B2(1,2-O2-4-ButC6H3) 2, B2(1,2-O2-3,5-But 2C 6H2)2, B2(1,2-O2-3-MeC6H3)2, B2(1,2-O2-4-MeC6H3)2, B2(1,2-O2-3-MeOC6H3)2, B2(1,2-S2C6H4)2, B2(1,2-S2-4-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH(CO 2Me)]2 affording analogous rhodium complexes all of which have been characterised spectroscopically. The complexes derived from the reactions with B2(1,2-O2C6H4)2 and B2(1,2-O2-3-MeC6H3)2 have also been characterised by X-ray crystallography, the structures comprising a five-co-ordinate rhodium centre with a square-based-pyramidal geometry in which the apical site is occupied by a boryl group and the phosphines are mutually trims in basal positions. Reactivity studies have also been carried out for [RhCl(PPh3)2\{B(1,2-O2C6H 4)\}2]. Hydrolysis or alcoholysis with catechol afforded [RhH2Cl(PPh3)3] and either B2(1,2-O2C6H4)2(μ-O) or B2(1,2-O2C6H4)3 and addition of the phosphines PMe3, PEt3 and PMe2Ph afforded the new bis(boryl) compounds cis,mer-[RhCl(PMe3)3\{B(1,2-O2C 6H4)\}2], [RhCl(PEt3)2-\{B(1,2-O2C6H 4)\}2] and cis,mer-[RhCl(PMe2Ph)3\{B(1,2-O2C 6H4)\}2], the PEt3 complex having been characterised by X-ray crystallography and shown to be similar to the PPh3 complex. The iridium analogue [IrCl(PEt3)2-\{B(1,2-O2C6H 4)\}2] was also prepared from the reaction between [IrCl(PEt3)3] and B2(1,2-O2C6H4)2 and shown by X-ray crystallography to be isomorphous with the rhodium complex. Reactions between [RhCl(PPh3)2-\{B(1,2-O2C6H 4)\}2] and the phosphines PPri 3, P(C6H11)3, 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) are also described although these do not result in new rhodium boryl complexes. The reaction between [\{RhCl(dppe)\}2] and B2(1,2-O2C6H4)2 afforded a compound tentatively assigned as [Rh(dppe)2\{B(1,2-O2C6H4)\}] with analogous compounds being formed with the diborane(4) compounds B2(1,2-O2-3-MeC6H3)2 and B2(1,2-O2-4-MeC6H3)2. Finally, the reaction between [Rh(PMe3)4]Cl and the diborane(4) compound B2(1,2-O2C6H4)2 is described which affords cis,mer-[RhCl(PMe3)3\{B(1,2-O2C 6H4)\}2]. Analogous reactions with B2(1,2-O2-3,5-But 2C 6H2)2, B2(1,2-O2-3-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH-(CO 2MeJ]2 afforded similar products.",

author = "William Clegg and Lawlor, \{Fiona J.\} and Marder, \{Todd B.\} and Paul Nguyen and Norman, \{Nicholas C.\} and Orpen, \{A. Guy\} and Quayle, \{Michael J.\} and Rice, \{Craig R.\} and Robins, \{Edward G.\} and Scott, \{Andrew J.\} and Souza, \{Fabio E.S.\} and Graham Stringer and Whittell, \{George R.\}",

year = "1998",

month = jan,

day = "21",

doi = "10.1039/A705374F",

language = "English",

pages = "301--309",

journal = "Journal of the Chemical Society - Dalton Transactions",

issn = "0300-9246",

publisher = "Royal Society of Chemistry",

number = "2",

}

TY - JOUR

T1 - Boron-boron bond oxidative addition to rhodium(I) and iridium(I) centres

AU - Clegg, William

AU - Lawlor, Fiona J.

AU - Marder, Todd B.

AU - Nguyen, Paul

AU - Norman, Nicholas C.

AU - Orpen, A. Guy

AU - Quayle, Michael J.

AU - Rice, Craig R.

AU - Robins, Edward G.

AU - Scott, Andrew J.

AU - Souza, Fabio E.S.

AU - Stringer, Graham

AU - Whittell, George R.

PY - 1998/1/21

Y1 - 1998/1/21

N2 - The reaction between the diborane(4) compound B2(1,2-O2C6H4)2 and either of the rhodium(I) complexes [RhCl(PPh3)3] or [{Rh(μ-Cl)(PPh3)2}2] afforded the colourless rhodium(III) bis(boryl) species [RhCl(PPh3)2-{B(1,2-O2C6H 4)}2]. Similar reactions have been carried out with the diborane(4) compounds B2(1,2-O2-4-ButC6H3) 2, B2(1,2-O2-3,5-But 2C 6H2)2, B2(1,2-O2-3-MeC6H3)2, B2(1,2-O2-4-MeC6H3)2, B2(1,2-O2-3-MeOC6H3)2, B2(1,2-S2C6H4)2, B2(1,2-S2-4-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH(CO 2Me)]2 affording analogous rhodium complexes all of which have been characterised spectroscopically. The complexes derived from the reactions with B2(1,2-O2C6H4)2 and B2(1,2-O2-3-MeC6H3)2 have also been characterised by X-ray crystallography, the structures comprising a five-co-ordinate rhodium centre with a square-based-pyramidal geometry in which the apical site is occupied by a boryl group and the phosphines are mutually trims in basal positions. Reactivity studies have also been carried out for [RhCl(PPh3)2{B(1,2-O2C6H 4)}2]. Hydrolysis or alcoholysis with catechol afforded [RhH2Cl(PPh3)3] and either B2(1,2-O2C6H4)2(μ-O) or B2(1,2-O2C6H4)3 and addition of the phosphines PMe3, PEt3 and PMe2Ph afforded the new bis(boryl) compounds cis,mer-[RhCl(PMe3)3{B(1,2-O2C 6H4)}2], [RhCl(PEt3)2-{B(1,2-O2C6H 4)}2] and cis,mer-[RhCl(PMe2Ph)3{B(1,2-O2C 6H4)}2], the PEt3 complex having been characterised by X-ray crystallography and shown to be similar to the PPh3 complex. The iridium analogue [IrCl(PEt3)2-{B(1,2-O2C6H 4)}2] was also prepared from the reaction between [IrCl(PEt3)3] and B2(1,2-O2C6H4)2 and shown by X-ray crystallography to be isomorphous with the rhodium complex. Reactions between [RhCl(PPh3)2-{B(1,2-O2C6H 4)}2] and the phosphines PPri 3, P(C6H11)3, 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) are also described although these do not result in new rhodium boryl complexes. The reaction between [{RhCl(dppe)}2] and B2(1,2-O2C6H4)2 afforded a compound tentatively assigned as [Rh(dppe)2{B(1,2-O2C6H4)}] with analogous compounds being formed with the diborane(4) compounds B2(1,2-O2-3-MeC6H3)2 and B2(1,2-O2-4-MeC6H3)2. Finally, the reaction between [Rh(PMe3)4]Cl and the diborane(4) compound B2(1,2-O2C6H4)2 is described which affords cis,mer-[RhCl(PMe3)3{B(1,2-O2C 6H4)}2]. Analogous reactions with B2(1,2-O2-3,5-But 2C 6H2)2, B2(1,2-O2-3-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH-(CO 2MeJ]2 afforded similar products.

AB - The reaction between the diborane(4) compound B2(1,2-O2C6H4)2 and either of the rhodium(I) complexes [RhCl(PPh3)3] or [{Rh(μ-Cl)(PPh3)2}2] afforded the colourless rhodium(III) bis(boryl) species [RhCl(PPh3)2-{B(1,2-O2C6H 4)}2]. Similar reactions have been carried out with the diborane(4) compounds B2(1,2-O2-4-ButC6H3) 2, B2(1,2-O2-3,5-But 2C 6H2)2, B2(1,2-O2-3-MeC6H3)2, B2(1,2-O2-4-MeC6H3)2, B2(1,2-O2-3-MeOC6H3)2, B2(1,2-S2C6H4)2, B2(1,2-S2-4-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH(CO 2Me)]2 affording analogous rhodium complexes all of which have been characterised spectroscopically. The complexes derived from the reactions with B2(1,2-O2C6H4)2 and B2(1,2-O2-3-MeC6H3)2 have also been characterised by X-ray crystallography, the structures comprising a five-co-ordinate rhodium centre with a square-based-pyramidal geometry in which the apical site is occupied by a boryl group and the phosphines are mutually trims in basal positions. Reactivity studies have also been carried out for [RhCl(PPh3)2{B(1,2-O2C6H 4)}2]. Hydrolysis or alcoholysis with catechol afforded [RhH2Cl(PPh3)3] and either B2(1,2-O2C6H4)2(μ-O) or B2(1,2-O2C6H4)3 and addition of the phosphines PMe3, PEt3 and PMe2Ph afforded the new bis(boryl) compounds cis,mer-[RhCl(PMe3)3{B(1,2-O2C 6H4)}2], [RhCl(PEt3)2-{B(1,2-O2C6H 4)}2] and cis,mer-[RhCl(PMe2Ph)3{B(1,2-O2C 6H4)}2], the PEt3 complex having been characterised by X-ray crystallography and shown to be similar to the PPh3 complex. The iridium analogue [IrCl(PEt3)2-{B(1,2-O2C6H 4)}2] was also prepared from the reaction between [IrCl(PEt3)3] and B2(1,2-O2C6H4)2 and shown by X-ray crystallography to be isomorphous with the rhodium complex. Reactions between [RhCl(PPh3)2-{B(1,2-O2C6H 4)}2] and the phosphines PPri 3, P(C6H11)3, 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) are also described although these do not result in new rhodium boryl complexes. The reaction between [{RhCl(dppe)}2] and B2(1,2-O2C6H4)2 afforded a compound tentatively assigned as [Rh(dppe)2{B(1,2-O2C6H4)}] with analogous compounds being formed with the diborane(4) compounds B2(1,2-O2-3-MeC6H3)2 and B2(1,2-O2-4-MeC6H3)2. Finally, the reaction between [Rh(PMe3)4]Cl and the diborane(4) compound B2(1,2-O2C6H4)2 is described which affords cis,mer-[RhCl(PMe3)3{B(1,2-O2C 6H4)}2]. Analogous reactions with B2(1,2-O2-3,5-But 2C 6H2)2, B2(1,2-O2-3-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH-(CO 2MeJ]2 afforded similar products.

UR - https://www.scopus.com/pages/publications/33748596872

U2 - 10.1039/A705374F

DO - 10.1039/A705374F

M3 - Article

AN - SCOPUS:33748596872

SN - 0300-9246

SP - 301

EP - 309

JO - Journal of the Chemical Society - Dalton Transactions

JF - Journal of the Chemical Society - Dalton Transactions

IS - 2

ER -

Boron-boron bond oxidative addition to rhodium(I) and iridium(I) centres

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