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Issue 12, 2015
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Organometallic chemistry of ethynyl boronic acid MIDA ester, HC[triple bond, length as m-dash]CB(O2CCH2)2NMe

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Abstract

The reactions of HC[triple bond, length as m-dash]CBMIDA (BMIDA = B(O2CCH2)2NMe) with a range of ruthenium complexes afford the first isolated examples of σ-alkynyl, σ-alkenyl and vinylidene complexes bearing 4-coordinate boron substituents. Specifically, the reactions of HC[triple bond, length as m-dash]CBMIDA with [RuH(S2CNR2)(CO)(PPh3)2] (R = Me, Et) and [Ru(CO)2(PPh3)3] afford the alkynyl complexes [Ru(C[triple bond, length as m-dash]CBMIDA)(S2CNR2)(CO)(PPh3)2] and [RuH(C[triple bond, length as m-dash]CBMIDA)(CO)2(PPh3)2], the latter being converted to [Ru(C[triple bond, length as m-dash]CBMIDA)Cl(CO)2(PPh3)2] on treatment with chloroform. With [RuCl(dppe)2]PF6 the vinylidene salt [RuCl([double bond, length as m-dash]C[double bond, length as m-dash]CHBMIDA)(dppe)2]PF6 is obtained, which reacts with Et3N to afford the neutral alkynyl derivative [Ru(C[triple bond, length as m-dash]CBMIDA)Cl(dppe)2]. Hydrometallation of HC[triple bond, length as m-dash]CBMIDA by [RuHCl(CO)(PPh3)3] affords the coordinatively unsaturated σ-alkenyl complex [RuCl(CH[double bond, length as m-dash]CHBMIDA)(CO)(PPh3)2] which in turn reacts with CO, CNC6H2Me3-2,4,6, [Et2NH2][S2CNEt2] or K[HB(pz)3] (pz = pyrazol-1-yl) to afford the coordinatively saturated complexes [Ru(CH[double bond, length as m-dash]CHBMIDA)Cl(CO)2(PPh3)2], [Ru(CH[double bond, length as m-dash]CHBMIDA)Cl(CO)(CNC6H2Me3)(PPh3)2], [Ru(CH[double bond, length as m-dash]CHBMIDA)(S2CNEt2)(CO)-(PPh3)2] and [Ru(CH[double bond, length as m-dash]CHBMIDA)(CO)(PPh3){HB(pz)3}]. In all cases, the transannular N→B dative bond is retained in the BMIDA substituent.

Graphical abstract: Organometallic chemistry of ethynyl boronic acid MIDA ester, HC [[triple bond, length as m-dash]] CB(O2CCH2)2NMe

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Publication details

The article was received on 03 Dec 2014, accepted on 19 Jan 2015 and first published on 19 Jan 2015


Article type: Paper
DOI: 10.1039/C4DT03695F
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 5713-5726
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    Organometallic chemistry of ethynyl boronic acid MIDA ester, HC[triple bond, length as m-dash]CB(O2CCH2)2NMe

    A. F. Hill, C. D. Stewart and J. S. Ward, Dalton Trans., 2015, 44, 5713
    DOI: 10.1039/C4DT03695F

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