Borazine complexes

Boron-bonded p -borazine complexes of transition metals have been prepared by two different approaches (a) nucleophilic substitution of B,fi, fi"-trichloro-borazine with an anionic metal carbonyl reagent and (b) oxidative addition of a B-Br bond of 5,5, B"-tribromoborazine to a zerovalent group 10 complex (see examples in Scheme 9.2). 

Catecholborane and its derivatives had a pivotal role in establishing the class of boryl complexes, since they proved to be the most versatile starting materials for the synthesis of such compounds. This was demonstrated in many works especially by Baker, Hartwig, Marder, Norman, and Smith. ia In the course of our investigations we aimed at boryl complexes with different substituents attached to boron, and we could show that boranes with B-N bonds are also very well suited for the synthesis of boryl complexes. Over the last three years a wide variety of products was obtained by salt elimination reactions between anionic transition metal complexes and haloboranes. Examples include aminoboryl- 4, 5, diborane(4)yl- 6, 7, and rj -borazine complexes 8 (Figure 4). 

Figure 4 Boryl complexes derived from N-substituted boranes aminoboryl complexes 4 and 5, diborane(4)yl complexes 6 and 7, rj -borazine complexes 8...

The electronic difference between benzene and borazine is further supported by the properties of compounds of the type (R<,BjN j)Cr(CO)j. Although the.se are formally analogous to (rj< -QRf,)Cr(CO)j. the bonding is not nearly so strong in the borazine complex—its ring-metal dissociation energy appears to be about one-half that of the arene complex. In addition, there is considerable evidence that the borazine molecule is puckered in the.sc complexes. The actual structure appears to be intermediate between a true tt complex and the extreme rr-only model ... 

Borazine decomposes slowly on storage and is hydrolyzed at elevated temperatures to NH3 and B(OH)3. It is of interest that borazine resembles benzene in forming arene-metal complexes (Section 23-3) thus the hexamethyl-borazine complex, B3N3(CH3)6Cr(CO)3 has been reported and closely resembles C6(CH3)6Cr(CO)3 but is thermally less stable.36... 

This works well for all nido- and arachno-boranes but not for the c/o o-dianions, which are much less reactive. Reactions of B2H6 with NH3 are complex and, depending on the conditions, yield aminodiborane, H2B(/r-H)(/r-NH2)BH2, or the diammoniate of diborane, [BH2(NH3)2]-[BH4] (p. 165) at higher temperatures the benzene analogue borazine, (HNBH)3, results (see p. 210). 

B-C bonds, 3, 97 B-N bonds, 3, 97 B-O bonds, 3,94 B-P bonds, 3, 97 B-Si bonds, 3, 97 oxo acid anion complexes, 3, 96 Borates, alkoxo-, 3, 94 Borates, amidotrihydro-, 3,92 Borates, aryloxo-, 3, 94 Borates, carboxylato-, 3,96 Borates, catechol, 3,95 Borates, chlorosulfato-, 3,97 Borates, dicarboxylato-, 3,96 Borates, dipyrazol-l-yl-, 3, 92 Borates, halogeno-, 3,92 Borates, halogenohydro-, 3,90 Borates, hydro-, 3,90 Borates, hydrohydroxo-, 3,90 Borates, hydropyrazol-l-yl-, 3, 92 Borates, hydroxo-, 3,94 Borates, hydroxycarboxylato-, 3,96 Borates, inositol, 3, 95 Borates, monoalkyl-, 3, 92 Borates, monophosphido-, 3, 92 Borates, peroxohydroxo-, 3, 94 Borates, polyol, 3, 95 Borates, pyrrol-l-yl-, 3, 92 Borates, sulfato-, 3, 97 Borates, tetrabromo-, 3, 92 Borates, tetrachloro-, 3, 92 Borates, tetrafluoro-, 3, 92 minerals, 6, 847 Borates, tetrahalogeno-mixed, 3, 93 nB NMR, 3, 92 Borates, tetraiodo-, 3, 92 Borates, tetranitrato-, 3, 96 Borates, tetraperchlorato-, 3, 97 Borates, tripyrazol-l-yl-, 3, 92 Borax, 3,101 Borazines... 

Borazine is isoelectronic and isostructural with benzene and may act as a six-electron donor in complex chemistry. In contrast to arene ligands of arene-transi-tion-metal complexes, coordinated borazines lose their planarity and are slightly puckered . Nevertheless, the B atoms show interactions with metal atoms. 

Though borazine itself gives no stable complexes, alkyl substituted derivatives are formed by the reaction of borazines with LjMfCO), (L = nitrile) (Table 1,... 

Equation (aj) also allows the synthesis of unsymmetrieally substituted borazines, e.g., (EtBMe2B2NjMe3)Cr(CO)3 or (PhBMe2B2N3Me3)Cr(CO)3 . The reactions take place in dioxane at 30-40°C with reduced pressure to pump off eliminated nitrile. The dioxane complexes (C4Hg02)2M2(C0)5 are intermediates. If liquid borazines are used additional solvent becomes unnecessary. 

Other unsaturated boron heterocycles, such as borazines and borabenzenes, form transition metal complexes with the expected nido geometry, as exemplified by compounds (Et3N3B3Et3)Cr(CO)3 (123) and (CBH5BPh)Mn(CO)s (110) (Fig. 29). 

Hunt s group (50, 51) have pioneered the application of the Cl source to organometallics such as the iron tricarbonyl complex of heptafulvene, whose electron impact spectrum shows (M—CO)+ as the heaviest ion, in contrast to the methane Cl spectrum with the ion as base peak. Boron hydrides (52) and borazine (53) have also been studied. The methane Cl spectrum of arenechromium and -molybdenum (54) show protonation at the metal giving a protonated parent or molecular ion. Risby et al. have studied the isobutane Cl mass spectra of lanthanide 2,2,6,6-tetramethylheptane-3,5-dionates[Ln(thd)3] (55) and 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-oetanedione [H(fod)] lanthanide complexes (56). These latter complexes have been suggested as a means of analysis for the lanthanide elements. 

The most characteristic reaction of amine boranes is their conversion into aminoboranes and, subsequently, to borazine at higher temperatures.9,17 For complexes of low stability, the transfer of H from the boron to the donor is a characteristic process,11 40 as in the utilization of diborane as an electrophilic reducing agent. The neutral complexes of boranes are fairly stable towards hydrolysis. The key step of the hydrolysis was formerly assumed to involve displacement of BH3 by a proton, whereas in recent studies ionic intermediates, containing five-coordinated boron (R3N—BH4) are also taken into consideration.41,42 The hydrolytic... 

The heterocyclic compounds occupy an important place amongst boron-containing ligands [8], It is well known that borazines, having a six-member ring, form ri6(7i)-complexes, for example 554 [953], It was recently shown that cr(B)-metal-coordinated compounds of type 555 may also be obtained on the basis of this ligand system [954a] ... 

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