The Sting of the Scorpion: A Metallaboratrane

Abstract

An unprecedented intramolecular B-H activation of a hydrotris(2-sulfanyl-1-methylimidazolyl)borate ligand coordinated to ruthenium has provided the first example of metallaboratranes. The remarkable ease with which the ruthenaboratrane 1 forms relative to the case with a hydrotris(pyrazolyl)borate ligand is a consequence of the lability of the chelation and the increased ring size of the chelates.

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

“…This is by no means unique, and SO 2 adducts with, for example, Pt(PR 3 ) 2 (R = cyclohexyl, tert-butyl) [317] or [PtX(C 6 H 2 {CH 2 N(CH 3 ) 2 } 2 -2,6-R-4)] (R = OH, X = Cl; R = H, X = Cl, Br, I) [318] are considered to contain respectively Pt(0) and Pt(II). Their reversible binding of SO 2 is more in accord with these OS than with ionic approximation towards Pt +2 The first structural identification of a TM → B donor-acceptor bond in the [Ru(CO)(P(C 6 H 5 ) 3 ){B(mt) 3 }] (B(mt) 3 = tris(methimazolyl)borane) metallaboratrane by Hill [321] in 1999 has rekindled interest in the field, which has seen spectacular progress in the intervening years when similar complexes of Co [322], Ni [323], and others have been synthesized. The TM → Z-type ligand interactions can be divided into two main classes: supported and unsupported by donor buttresses, Fig.…”

“…[328], of Pt less Allen-electronegative than Ga (bottom) [332]. Left: supported, with octahedrally coordinated Ru [321]. Right: supported, with square-planar Au [149].…”

Strong agostic-type interactions in ruthenium benzylidene complexes containing 7-azaindole based scorpionate ligands

“…We have carried out a number of investigations on the relatively new ligand Tai 14 3 ], a flexible analogue of Trofimenko's ubiquitous ligand, Tp [Tp = hydrotris(pyrazolyl)borate]. 15 To date, little investigation has been carried out on Tai.…”

η1:η2-P-Pyrazolylphosphaalkene Complexes of Ruthenium(0)

“…Indeed, as was previously noted for 2a-b and 3a-b, the magnitude of the 1 J CH coupling (~130-140 Hz) is intermediate between those of C 2 H 4 (156 Hz) and CH 4 (125 Hz) [41], while 1 J PC are essentially unperturbed from those of the parent phosphaalkenyls, consistent with the case of a π-bound phosphaalkene. This scenario is further supported by a significant reduction in ν CO for the retained carbonyl (1900-1910 cm −1 ), indicative of increased density at metal and, on the basis of calculated force constants, consistent with reduction of the metal to Ru(0) [42][43][44][45][46].…”

“…reduction in νCO for the retained carbonyl (1900-1910 cm −1 ), indicative of increased density at metal and, on the basis of calculated force constants, consistent with reduction of the metal to Ru(0) [42][43][44][45][46]. Though augmented by computational data, the direct structural characterization of η 2 -pyrazolylphosphaalkene complexes has been limited previously to the single crystal X-ray structure of pyrazole derivative 2a and a low-quality structure of 3a that served to confirm connectivity [30].…”