Dynamic titanium phosphinoamides as unique bidentate phosphorus ligands for platinum

Hideo Nagashima, Takashi Sue, Takashi Oda, Akira Kanemitsu, Taisuke Matsumoto, Yukihiro Motoyama, Yusuke Sunada

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Treatment of lithium phosphinoamides, Ph2PN(Li)R [R = tBu, iPr], with TiCl4 results in formation of titanium phosphinoamides, (Ph2PNR)2TiCl2 [R = tBu (1a), iPr (1b)]. Crystallographic studies show that there are covalent bonds between the titanium and two nitrogen atoms, whereas two phosphorus atoms are coordinated to the metal center intramolecularly. Variable-temperature NMR studies suggest reversible dissociation of the phosphorus moieties from the titanium in solution. The dissociated phosphorus moieties are effectively captured by Pt(II) species; reactions of 1a with either (η4-COD)PtCl2, (η4-COD)Pt(R)(Cl) (R = Me, p-Tol), or [Me2Pt(μ-SMe2)]2 afford the corresponding Ti-Pt heterobimetallic complexes. The molecular structures of these complexes reveal that they have a six-membered dimetallacycle, in which a titanium and a platinum are connected by two bridging phosphinoamide ligands; the Pt-Ti distances indicate the existence of a Pt→Ti dative bond. The conformation of the dimetallacycle is a boat form, with two metals at the bow and the stem in the crystal; however, dynamic conformational change involving cleavage and re-formation of the Pt→Ti dative bond is indicated from variable-temperature NMR studies.

Original languageEnglish
Pages (from-to)1987-1994
Number of pages8
JournalOrganometallics
Volume25
Issue number8
DOIs
Publication statusPublished - Apr 10 2006

Fingerprint

Titanium
Platinum
Phosphorus
phosphorus
platinum
titanium
Ligands
ligands
crack opening displacement
Metals
Nuclear magnetic resonance
Atoms
nuclear magnetic resonance
Covalent bonds
covalent bonds
boats
Boats
bows
Lithium
stems

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Nagashima, H., Sue, T., Oda, T., Kanemitsu, A., Matsumoto, T., Motoyama, Y., & Sunada, Y. (2006). Dynamic titanium phosphinoamides as unique bidentate phosphorus ligands for platinum. Organometallics, 25(8), 1987-1994. https://doi.org/10.1021/om0509600

Dynamic titanium phosphinoamides as unique bidentate phosphorus ligands for platinum. / Nagashima, Hideo; Sue, Takashi; Oda, Takashi; Kanemitsu, Akira; Matsumoto, Taisuke; Motoyama, Yukihiro; Sunada, Yusuke.

In: Organometallics, Vol. 25, No. 8, 10.04.2006, p. 1987-1994.

Research output: Contribution to journalArticle

Nagashima, H, Sue, T, Oda, T, Kanemitsu, A, Matsumoto, T, Motoyama, Y & Sunada, Y 2006, 'Dynamic titanium phosphinoamides as unique bidentate phosphorus ligands for platinum', Organometallics, vol. 25, no. 8, pp. 1987-1994. https://doi.org/10.1021/om0509600
Nagashima, Hideo ; Sue, Takashi ; Oda, Takashi ; Kanemitsu, Akira ; Matsumoto, Taisuke ; Motoyama, Yukihiro ; Sunada, Yusuke. / Dynamic titanium phosphinoamides as unique bidentate phosphorus ligands for platinum. In: Organometallics. 2006 ; Vol. 25, No. 8. pp. 1987-1994.
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