Add time:09/02/2019         Source:sciencedirect.com

Reaction of fac-[RuCl3(NO)(P–N)] (1) with the triarylphosphines PR3 in MeOH allows for isolation of the monocationic Ru(II) complexes [RuCl2(NO)(P–N)(PR3)]PF6; P–N = o-diphenylphosphino-N,N-dimethylaniline, and R = p-MeO-C6H4 (complex 2), p-Me-C6H4 (3), Ph (4), and p-F-C6H4 (5). The complexes were characterized by elemental analysis, 31P{1H}, 1H NMR and IR spectroscopies, ESI-MS, CV, and X-ray structural data for complexes 3–5. The 31P{1H} spectra display two doublets with 2Jpp values consistent with cis P-atoms. The ESI-MS spectra reveal the molecular ion [RuCl2(NO)(P–N)(PR3)]+ and the fragmentation ions [M−PR3]+, [M−PR3−Cl]+, and [M−PR3−2Cl]+. CV data show a one-electron, quasi-reversible reduction process centred at the Ru–NO unit that depends on the pKa of the PR3. The IR spectra reveal νNO bands for coordinated NO+. A known, empirical inverse correlation between the δP value and the Ru–P bond length of the P–N ligand that exists for a series of cis- and trans-RuX2(L)(P–N)(PR3) complexes (X = Cl or Br), where L is a range of small molecules, is extended with L = NO+ and now covers the respective ranges of about 30–80 ppm and 2.39–2.17 Å.

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