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.
To preempt the emergence of conflicting assignments of d
n
configurations for metallaboratranes, it is recommended that line formulas include a superscript denoting the total number of electrons associated with the metal d orbitals and the M→B bond: viz., [Os(CO)(PPh3){B(mt)3](Os→B)
8
, [IrH(CO)(PPh3){HB(mt)2}](Ir→B)
8
, [RhCl(DMAP){BPh(C6H4P
i
Pr2)2}](Rh→B)
8
, [PtI2{B(mt)3}](Pt→B)
8
, and [Pt(PPh3){B(mt)3}](Pt→B)
10
(mt = methimazolyl, DMAP = (dimethylamino)pyridine).
The syntheses and reactivity of the first rhodaboratranes, [RhX(PPh 3 ){B(mt) 3 }] (X ) Cl, H) and -C 8 H 12 ){B(mt) 3 }]Cl, are described in detail together with preliminary investigations of the mechanistic processes involved. The subsequent exploitation and circumvention of the lability of [RhCl(PPh 3 ){B(mt) 3 }] in the synthesis of a range of isonitrile, [Rh(CNR)(PPh 3 ){B(mtand dialkyldithiocarbamate, [Rh(S 2 -NEt 2 ){B(mt) 3 }]Cl, complexes is described, along with the attempted synthesis of [Rh(CN t Bu) 2 {B(mt) 3 }]Cl from [Rh(η 4 -C 8 H 12 ){B(mt) 3 }]Cl. Single-crystal X-ray structure determinations of [Rh(L)(L′){B(mt) 3 }]-Cl (L ) CN t Bu, CN(C 6 H 3 Me 2 -2,6), L′ ) PPh 3 ; L ) L′ ) PMe 3 ) are reported.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.