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E-Selective Synthesis and Coordination Chemistry of Pyridine-Phosphaalkenes: Five Ligands Produce Four Distinct Types of Ru(II) Complexes.


ABSTRACT: Pyridine-phosphaalkene (PN) ligands 2a-e were prepared in an E-selective fashion using phospha-Wittig methodology. Treatment of these five ligands, varying only in their 6-substituent with RuCl2(PPh3)3, produced four distinct types of coordination complexes: pyridine-phosphaalkene-derived 3b,d, cyclized 4e, and six-coordinate 5a and 6c. Prolonged heating of 3b,d in THF resulted in C-H activation of the Mes* group and cyclization to give 4b,d featuring a bidentate pyridine-phospholane ligand bound to the metal center. Complex 5a, also possessing a newly formed phospholane ring, contained a different spatial arrangement of donors to Ru(II) with an agostic Ru-H-C interaction serving as the sixth donor to the transition metal center. Ligands 2b,d,e and Ru(II) complexes 3b, 4b,e and 5a were all characterized by X-ray crystallography. Six-coordinate 6c featured a structure similar to 4b,d,e, but with the CF3 substituent acting as a weakly bound sixth ligand to the Ru(II) center, as observed by 31P{1H} and19F NMR spectroscopy. The calculated structure of 6c established that the closest Ru- - -F contact was at 2.978 Å.

SUBMITTER: Nakashige ML 

PROVIDER: S-EPMC7723345 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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<i>E</i>-Selective Synthesis and Coordination Chemistry of Pyridine-Phosphaalkenes: Five Ligands Produce Four Distinct Types of Ru(II) Complexes.

Nakashige Mika L ML   Loristo Jarin I P JIP   Wong Lesley S LS   Gurr Joshua R JR   O'Donnell Timothy J TJ   Yoshida Wesley Y WY   Rheingold Arnold L AL   Hughes Russell P RP   Cain Matthew F MF  

Organometallics 20190822 17


Pyridine-phosphaalkene (PN) ligands <b>2a-e</b> were prepared in an <i>E</i>-selective fashion using phospha-Wittig methodology. Treatment of these five ligands, varying only in their 6-substituent with RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub>, produced four distinct types of coordination complexes: pyridine-phosphaalkene-derived <b>3b,d</b>, cyclized <b>4e</b>, and six-coordinate <b>5a</b> and <b>6c</b>. Prolonged heating of <b>3b,d</b> in THF resulted in C-H activation of the Mes* group a  ...[more]

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