Synthesis and structural characterization of [κ3-B,S,S- B(mimR)3]Ir(CO)(PPh3)H (R = But, Ph) and [κ4-B(mimBut)3]M(PPh3)Cl (M = Rh, Ir): Analysis of the bonding in metal borane compounds

Victoria K. Landry, Jonathan G. Melnick, Daniela Buccella, Keliang Pang, Joseph C. Ulichny, Gerard Parkin

Research output: Contribution to journalArticle

Abstract

A series of iridium and rhodium complexes that feature M→B dative bonds, namely [κ3-B,S,S-B(mimR)3]Ir(CO)- (PPh3)H (R = But, Ph) and [κ4-B(mim But)3]M(PPh3)CI (M = Rh, Ir), has been synthesized via (i) the reactions of Ir(PPh3)2(CO)Cl with [TmBut]TI and [TmPh]Li and (ii) the reactions of (COD)M(PPh3)Cl with [TmBut]K. The complexes have been structurally characterized by X-ray diffraction, thereby demonstrating the presence of a M→B dative bond in each complex. The nature of the M→B interaction in these complexes has been addressed by computational methods which indicate that the metal centers possess a d6 configuration. The d6 configuration is in accord with the value predicted by using a method that employs the valence to determine dn, but is not in accord with the d8 configuration that is predicted using the oxidation number. Thus, even though B(mimR)3 may be regarded as a neutral closed-shell ligand, coordination to a dn transition metal via the boron results in the formation of a complex in which the metal center possesses a dn-2 configuration.

Original languageEnglish (US)
Pages (from-to)2588-2597
Number of pages10
JournalInorganic Chemistry
Volume45
Issue number6
DOIs
StatePublished - Mar 20 2006

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Boranes
boranes
Carbon Monoxide
Metals
Iridium
Rhodium
Boron
synthesis
Computational methods
configurations
metals
Transition metals
Ligands
X ray diffraction
Oxidation
crack opening displacement
iridium
rhodium
boron
transition metals

ASJC Scopus subject areas

  • Inorganic Chemistry

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Synthesis and structural characterization of [κ3-B,S,S- B(mimR)3]Ir(CO)(PPh3)H (R = But, Ph) and [κ4-B(mimBut)3]M(PPh3)Cl (M = Rh, Ir) : Analysis of the bonding in metal borane compounds. / Landry, Victoria K.; Melnick, Jonathan G.; Buccella, Daniela; Pang, Keliang; Ulichny, Joseph C.; Parkin, Gerard.

In: Inorganic Chemistry, Vol. 45, No. 6, 20.03.2006, p. 2588-2597.

Research output: Contribution to journalArticle

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abstract = "A series of iridium and rhodium complexes that feature M→B dative bonds, namely [κ3-B,S,S-B(mimR)3]Ir(CO)- (PPh3)H (R = But, Ph) and [κ4-B(mim But)3]M(PPh3)CI (M = Rh, Ir), has been synthesized via (i) the reactions of Ir(PPh3)2(CO)Cl with [TmBut]TI and [TmPh]Li and (ii) the reactions of (COD)M(PPh3)Cl with [TmBut]K. The complexes have been structurally characterized by X-ray diffraction, thereby demonstrating the presence of a M→B dative bond in each complex. The nature of the M→B interaction in these complexes has been addressed by computational methods which indicate that the metal centers possess a d6 configuration. The d6 configuration is in accord with the value predicted by using a method that employs the valence to determine dn, but is not in accord with the d8 configuration that is predicted using the oxidation number. Thus, even though B(mimR)3 may be regarded as a neutral closed-shell ligand, coordination to a dn transition metal via the boron results in the formation of a complex in which the metal center possesses a dn-2 configuration.",
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