ABSTRACT
The oxoboryl complex trans-[(Cy3 P)2 BrPt(B≡O)] (2) reacts with the Groupâ 13 Lewis acids EBr3 (E=Al, Ga, In) to form the 1:1 Lewis acid-base adducts trans-[(Cy3 P)2 BrPt(B≡OEBr3 )] (6-8). This reactivity can be extended by using two equivalents of the respective Lewis acid EBr3 (E=Al, Ga) to form the 2:1 Lewis acid-base adducts trans-[(Cy3 P)2 (Br3 Al-Br)Pt(B≡OAlBr3 )] (18) and trans-[(Cy3 P)2 (Br3 Ga-Br)Pt(B≡OGaBr3 )] (15). Another reactivity pattern was demonstrated by coordinating two oxoboryl complexes 2 to InBr3 , forming the 1:2 Lewis acid-base adduct trans-[{(Cy3 P)2 BrPt(B≡O)}2 InBr3 ] (20). It was also possible to functionalize the B≡O triple bond itself. Trimethylsilylisothiocyanate reacts with 2 in a 1,2-dipolar addition to form the boryl complex trans-[(Cy3 P)2 BrPt{B(NCS)(OSiMe3 )}] (27).
ABSTRACT
New metal-only Lewis pairs (MOLPs: RuâCr and OsâCr) are prepared by the insertion of a zerovalent ruthenium or osmium complex into chromium-boron double bonds of borylene complexes. The reaction creates new borylene complexes (the first ever for osmium), and is crystallization-controlled; re-dissolving the complexes results in regeneration of the starting materials. A mechanism is proposed based on DFT calculations, along with a computational study of the unusual MOLPs.
ABSTRACT
Mono- and dinuclear hydridoborylene complexes were prepared by intermetallic borylene transfer from Group VI borylene or metalloborylene reagents. The hydride and borylene ligands were found to interact with each other significantly, although the boron ligand retains much of its former borylene character. Zero-valent platinum fragments were successively added to the dinuclear hydridoborylene complexes, resulting in tri- and tetranuclear borido complexes, in which the B-H interaction has been lost, and the hydride ligands now bridge two metal centers. The complexes were studied spectroscopically, crystallographically, and by DFT methods, and the unusual bonding situation in the M-B-H triangles of hydridoborylene complexes were evaluated.
ABSTRACT
The platinum(0) monocarbonyl complex, [(Cy(3)P)(2)Pt(CO)], was synthesized by reaction of [(Cy(3)P)(2)Pt] with [(η(5)-C(5)Me(5))Ir(CO)(2)] and subsequent irradiation. X-ray structure analysis was performed and represents the first structural evidence of a platinum(0) monocarbonyl complex bearing two free phosphine ligands. Its corresponding dicarbonyl complex [(Cy(3)P)(2)Pt(CO)(2)] was synthesized by treatment of [(Cy(3)P)(2)Pt] with CO at -40 °C and confirmed by X-ray structure analysis.
