NDLI: PNP-Ligated Heterometallic Rare-Earth/Ruthenium Hydride Complexes Bearing Phosphinophenyl and Phosphinomethyl Bridging Ligands

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PNP-Ligated Heterometallic Rare-Earth/Ruthenium Hydride Complexes Bearing Phosphinophenyl and Phosphinomethyl Bridging Ligands

Content Provider	Semantic Scholar
Author	O. Wylie W. N. Kang, Xiaohui Hou, Zhaomin
Copyright Year	2014
Abstract	The reaction of rare-earth bis(alkyl) complexes containing a bis(phosphinophenyl)amido pincer (PNP), LnPNPiPr(CH2SiMe3)2 (1-Ln, Ln = Y, Ho, Dy), with ruthenium trihydride phosphine complexes, Ru(C5Me5)H3PPh3 and Ru(C5Me5)H3PPh2Me, gave the corresponding bimetallic Ln/Ru complexes bearing two hydride ligands and a bridging phosphinophenyl (μ-C6H4PPh2-κP:κC1, 2a-Ln) or a bridging phosphinomethyl ligand (μ-CH2PPh2-κP:κC, 2b-Ln), respectively. Reaction of 2a-Y with CO gas at 1 atm and at 20 °C in toluene-d8 afforded the complex 3a-Y, which bears a bridging pseudooxymethylene ligand (μ-OCH(o-C6H4)PPh2-κP:κO) and a bridging hydride ligand on the Y/Ru centers. Computational studies by the DFT method suggested that 3a-Y was formed in two steps: first the coordination of CO (ΔG(B3PW91) = 22.9; ΔG(M06) = 14.9 kcal/mol) and migratory insertion of the Y–C6H4 group (ΔG⧧(B3PW91) = 13.3; ΔG⧧(M06) = 16.7 kcal/mol), followed by a rapid intramolecular hydride migration to the resulting acyl group. Complex 2b-Y reacted with...
Starting Page	1030
Ending Page	1043
Page Count	14
File Format	PDF HTM / HTML
DOI	10.1021/om401216v
Alternate Webpage(s)	http://www.riken.jp/lab-www/organometallic/HP2015/img/1030-1043.pdf
Alternate Webpage(s)	https://doi.org/10.1021/om401216v
Volume Number	33
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article

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