Diphosphaborane and Metalladiphosphaborane: Ligands for Transition‐Metal Chemistry

The molecular structures of 1,2-closo-P(2)B(10)H(10) (1) and 1,2-closo-As(2)B(10)H(10) (2) have been determined by gas electron diffraction and the results obtained compared with those from computation at the MP2/6-31G** level of theory. The level of agreement is good for 2 (root-mean-square [rms] misfit for As and B atoms 0.0297 Å) and very good for 1 (rms misfit for P and B atoms 0.0082 Å). In comparing the structures of 1 and 2 with that of 1,2-closo-C(2)B(10)H(12) (I) it is evident that expansion of the polyhedron from I to 1 to 2 is restricted only to the heteroatom vertices and the B(6) face to which these are bound. Following deboronation (at B3) and subsequent metallation, compounds 1 and 2 have been converted into the new metalladiheteroboranes 3-(η-C(9)H(7))-3,1,2-closo-CoAs(2)B(9)H(9) (4), 3-(η-C(10)H(14))-3,1,2-closo-RuAs(2)B(9)H(9) (5), 3-(η-C(5)H(5))-3,1,2-closo-CoP(2)B(9)H(9) (6), 3-(η-C(9)H(7))-3,1,2-closo-CoP(2)B(9)H(9) (7) and 3-(η-C(10)H(14))-3,1,2-closo-RuP(2)B(9)H(9) (8), the last three constituting the first examples of metalladiphosphaboranes. Together with the known compound 3-(η-C(5)H(5))-3,1,2-closo-CoAs(2)B(9)H(9) (3), compounds 4-8 have been analysed by NMR spectroscopy and (except for 8) single-crystal X-ray diffraction. The (11)B NMR spectra of analogous pairs of metalladiphosphaborane and metalladiarsaborane (6 and 3, 7 and 4, 8 and 5) reveal a consistently narrower (9-10 ppm) chemical shift range for the metalladiarsaboranes, the combined result of a deshielding of the lowest frequency resonance (B6) and an increased shielding of the highest frequency resonance (B8) via an antipodal effect. In crystallographic studies, compounds 3 and 5B (one of two crystallographically-independent molecules) suffer As/B disorder, but in both cases it was possible to refine distinct, ordered, components of the disorder, the first time this has been reported for metalladiarsaboranes. Moreover, whilst the Cp compounds 6 and 3 are disordered, their indenyl analogues 7 and 4 are either ordered or significantly less disordered, a consequence of both the reduced symmetry of an indenyl ligand compared to a Cp ligand and the preference of the former for a distinct conformation relative to the cage heteroatoms. Unexpectedly, whilst this conformation in the cobaltadiphosphaborane 7 is cis-staggered (similar to that previously established for the analogous cobaltadicarborane), in the cobaltadiarsaborane 4 the conformation is close to cis-eclipsed.

show abstract

“…Further chromatography in pure CH 2 Cl 2 yielded a second product which will be reported separately. 29 For 8: 11…”

Section: -(G-c 5 H 5 )-312-closo-cop 2 B 9 H 9 (6)mentioning

confidence: 99%

New chemistry of 1,2-closo-P2B10H10 and 1,2-closo-As2B10H10; in silico and gas electron diffraction structures, and new metalladiphospha- and metalladiarsaboranes

et al. 2011

View full text Add to dashboard Cite

show abstract

Phosphorus as Lone Pair Donor and Ligand Acceptor: A Paddlewheel with Ru←P Axis

Gericke

Wagler

2018

Eur J Inorg Chem

View full text Add to dashboard Cite

[Ru(PyO) 2 (nbd)] (1) (PyO = 2-pyridyloxy, nbd = norbornadiene) and PhP(PyO) 2 react with formation of complex [PhP(μ-PyO) 3 Ru(κ-PyO)] (2), which features a Ru-P bond between a pentacoordinate P atom and a hexacoordinate Ru atom, bridged by three PyO ligands. Addition of CO leads to opening of the Ru(κ-PyO) chelate with formation of complex [PhP(μ-PyO) 4 Ru(CO)] (3), a paddlewheel-shaped complex with a Ru-P bond between a hexacoordinate P atom and a hexacoor-

show abstract

Diphosphaborane and Metalladiphosphaborane: Ligands for Transition‐Metal Chemistry

Cited by 2 publications

References 26 publications

New chemistry of 1,2-closo-P2B10H10 and 1,2-closo-As2B10H10; in silico and gas electron diffraction structures, and new metalladiphospha- and metalladiarsaboranes

New chemistry of 1,2-closo-P2B10H10 and 1,2-closo-As2B10H10; in silico and gas electron diffraction structures, and new metalladiphospha- and metalladiarsaboranes

Phosphorus as Lone Pair Donor and Ligand Acceptor: A Paddlewheel with Ru←P Axis

Contact Info

Product

Resources

About