Bis-catecholate, bis-dithiocatecholate, and tetraalkoxy diborane(4) compounds: Aspects of synthesis and electronic structure

被引:65
作者
Lawlor, FJ
Norman, NC
Pickett, NL
Robins, EG
Nguyen, P
Lesley, G
Marder, TB
Ashmore, JA
Green, JC
机构
[1] Newcastle Univ, Dept Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England
[2] Univ Waterloo, Dept Chem, Waterloo, ON N2L 3G1, Canada
[3] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England
关键词
D O I
10.1021/ic980425a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis and characterization of a series of bis-catecholate diborane(4) compounds, B-2(1,2-O2C6H4)(2) (3), B-2(1,2-O-2-3-MeC6H3)(2) (6), B-2(1,2-O-2-4-MeC6H3)(2) (7), B-2(1,2-O-2-4-(BuC6H3)-C-t)(2) (8), B-2(1,2-O-2-3,5-(Bu2C6H2)-C-t)(2) (9), B-2(1,2-O-2-3-MeOC6H3)(2) (10), bis-ditkiocatecholate diborane(3) compounds, B-2(1,2-S2C6H4)(2) (13), B-2(1,2-S-2-4-MeC6H3)(2) (14), and tetraalkoxy diborane(4) compounds, B-2(OCH2CMe2CH2O)(2) (11) and B-2(OCMe2CMe2O)(2) (12) from B-2(NMe2)(4) (1) is described, as are the bis(NHMe2) adducts or 3 and 9, namely [B-2(1,1-O2C6H4)(2)-(NHMe2)(2)] (1) and [B-2(1,2-O-2-3,5-(Bu2C6H2)-C-t)(2)(NHMe2)(2)] (5). The latter two compounds are intermediates in thr formation of 3 and 9 from 1. Compound 1 is synthesized by reductive coupling of BCl(NMe2)(2), which in turn is prepared from reaction of BCl3 with B(NMe2)(3) in a 1:2 stoichiometry. We have also tharacterized [B2Cl4- (NHMe2)(2)] (15) formed from addition of HCl to 1 prior to complete reaction with diols, and the salt, [NH2Me2][B(1,2-O2C6H3)(2)] (16) which arises from addition of catechol to B(NMe2)(3). Thus, any B(NMe2)(3) impurity present after the preparation of 1 needs to be removed by distillation prior to reaction with alcohols. The dimer, [BCl2-(mu-NMe2)](2) (17) has also been characterized. This is formed from reaction of BCl3 with B(NMe2)(3) if a 2:1 rather than 1:2 stoichiometry is used. Photoelectron spectra of 1, 3, 8, 11, and 12 are reported along with those of the corresponding diols, catechol, 4-Bu-t-catechol, 2,2-dimethyl-1,3-propanediol. and pinacol. The ionization energies of the B-2(OR)(4) compounds follow the series 8 < 3 < 12 < 11. Replacement of O for N in the B2N4 framework increases the IE by ca. 1.65 eV, whereas the presence of an aromatic ring rather than an aliphatic chain decreases the IE by ca. 1.50 eV. The presence of electron donating Bu-t-gr oups also decreases the IE.
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页码:5282 / 5288
页数:7
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