Cleavage of dinitrogen to yield a (t-BuPOCOP)molybdenum(IV) nitride.

(t-BuPOCOP)MoI(2) (1; t-BuPOCOP = C(6)H(3)-1,3-[OP(t-Bu)(2)](2)) has been synthesized from MoI(3)(THF)(3). Upon reduction of 1 with Na/Hg under dinitrogen molecular nitrogen is cleaved to form [(t-BuPOCOP)Mo(I)(N)](-). The origin of the N atom was confirmed using (15)N(2).

Dihydrogen/dihydride or tetrahydride? An experimental and computational investigation of pincer iridium polyhydrides.

The iridium pincer complexes (PCP)IrH(4) (1; PCP = [kappa(3)-1,3-(CH(2)P(t)Bu(2))(2)C(6)H(3)]) and (POCOP)IrH(4) (2; POCOP = [kappa(3)-1,3-(OP(t)Bu(2))(2)C(6)H(3)]) have proven to be effective catalyst precursors for dehydrogenation of alkanes. The complex (POCOP)IrH(2) has also been applied successfully as a catalyst for release of H(2) from ammonia borane. Investigation of the "tetrahydride" forms of these complexes by solution NMR methods suggests their formulation as dihydrogen/dihydride species.

Sigma-borane complexes of iridium: synthesis and structural characterization.

Reaction of NaBH4 with (tBuPOCOP)IrHCl affords the previously reported complex (tBuPOCOP)IrH2(BH3) (1) (tBuPOCOP = kappa(3)-C6H3-1,3-[OP(tBu)2]2). The structure of 1 determined from neutron diffraction data contains a B-H sigma-bond to iridium with an elongated B-H bond distance of 1.45(5) A.

Efficient catalysis of ammonia borane dehydrogenation.

In the presence of an iridium pincer complex, dehydrogenation of ammonia borane (H3NBH3) occurs rapidly at room temperature in tetrahydrofuran to generate 1.0 equivalent of H2 and [NH2BH2]5. A metal borohydride complex has been isolated as a dormant form of the catalyst which can be reactivated by reaction with H2.

A dinucleating ligand related to the beta-diketiminates.

A new ligand conceptually creates two sites reminiscent of beta-diketiminates, and upon deprotonation the salts exist in oligomeric forms with potassium ions linking multiple ligands.