Zirconium(IV) tris(phosphinoamide) complexes as a tripodal-type metalloligand: A route to Zr-M (M = Cu, Mo, Pt) heterodimetallic complexes

Takashi Sue, Yusuke Sunada, Hideo Nagashima

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Abstract

Treatment of ZrCl4 with 3 equiv. of Li(PPh2NR) (R = tBu, iPr) gives tris(phosphinoamide)zirconium complexes, (PPh 2NR)3-ZrCl [R = tBu (1a), iPr (1b)], in high yield. Crystal structures of 1a,b show that three phosphorus atoms are coordinated to the zirconium center in the solid state, whereas variable temperature NMR studies indicate a reversible coordination/dissociation process of three phosphorus atoms in the solution state. Reaction of 1a,b with CuCl give rise to the formation of Zr-Cu heterodimetallic complexes, ClCu(Ph2PNR) 3-ZrCl [R = tBu (2a), iPr (2b)]. The molecular structures of 2a,b show that the Cu atom adopts a pseudotetrahedral coordination geometry with tripodal phosphorus moieties and a chlorine atom, whereas the ligand arrangement around the Zr atom is trigonal bipyramidal with the linear Cl-Zr-Cu axis at the apical site. A Zr-Mo heterodimetallic complex, (CO)3-Mo(Ph 2PNiPr)3ZrCl (3), is synthesized from 1b and Mo(CO) 3-(CH3CN)3, in which the ligands around the Mo center are arranged octahedrally, and three phosphorus moieties are coordinated in the fac-P3 fashion. The reaction of 1b with a square planar PtII precursor, such as (COD)PtCl2, is unique and gives (κ2-Ph2PNiPr)Pt(Ph2PNiPr) 2ZrCl3 (4), which is the first example of a Zr-Pt zwitterionic heterodimetallic complex. The reaction involves intramolecular migration of two chlorine atoms from Pt to Zr as well as that of a Ph 2PNiPr moiety from Zr to Pt.

Original languageEnglish
Pages (from-to)2897-2908
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Issue number18
DOIs
Publication statusPublished - Jul 20 2007

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Atoms
Phosphorus
Chlorine
Ligands
Molecular structure
Crystal structure
Nuclear magnetic resonance
Geometry
Temperature

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

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title = "Zirconium(IV) tris(phosphinoamide) complexes as a tripodal-type metalloligand: A route to Zr-M (M = Cu, Mo, Pt) heterodimetallic complexes",
abstract = "Treatment of ZrCl4 with 3 equiv. of Li(PPh2NR) (R = tBu, iPr) gives tris(phosphinoamide)zirconium complexes, (PPh 2NR)3-ZrCl [R = tBu (1a), iPr (1b)], in high yield. Crystal structures of 1a,b show that three phosphorus atoms are coordinated to the zirconium center in the solid state, whereas variable temperature NMR studies indicate a reversible coordination/dissociation process of three phosphorus atoms in the solution state. Reaction of 1a,b with CuCl give rise to the formation of Zr-Cu heterodimetallic complexes, ClCu(Ph2PNR) 3-ZrCl [R = tBu (2a), iPr (2b)]. The molecular structures of 2a,b show that the Cu atom adopts a pseudotetrahedral coordination geometry with tripodal phosphorus moieties and a chlorine atom, whereas the ligand arrangement around the Zr atom is trigonal bipyramidal with the linear Cl-Zr-Cu axis at the apical site. A Zr-Mo heterodimetallic complex, (CO)3-Mo(Ph 2PNiPr)3ZrCl (3), is synthesized from 1b and Mo(CO) 3-(CH3CN)3, in which the ligands around the Mo center are arranged octahedrally, and three phosphorus moieties are coordinated in the fac-P3 fashion. The reaction of 1b with a square planar PtII precursor, such as (COD)PtCl2, is unique and gives (κ2-Ph2PNiPr)Pt(Ph2PNiPr) 2ZrCl3 (4), which is the first example of a Zr-Pt zwitterionic heterodimetallic complex. The reaction involves intramolecular migration of two chlorine atoms from Pt to Zr as well as that of a Ph 2PNiPr moiety from Zr to Pt.",
author = "Takashi Sue and Yusuke Sunada and Hideo Nagashima",
year = "2007",
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T1 - Zirconium(IV) tris(phosphinoamide) complexes as a tripodal-type metalloligand

T2 - A route to Zr-M (M = Cu, Mo, Pt) heterodimetallic complexes

AU - Sue, Takashi

AU - Sunada, Yusuke

AU - Nagashima, Hideo

PY - 2007/7/20

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N2 - Treatment of ZrCl4 with 3 equiv. of Li(PPh2NR) (R = tBu, iPr) gives tris(phosphinoamide)zirconium complexes, (PPh 2NR)3-ZrCl [R = tBu (1a), iPr (1b)], in high yield. Crystal structures of 1a,b show that three phosphorus atoms are coordinated to the zirconium center in the solid state, whereas variable temperature NMR studies indicate a reversible coordination/dissociation process of three phosphorus atoms in the solution state. Reaction of 1a,b with CuCl give rise to the formation of Zr-Cu heterodimetallic complexes, ClCu(Ph2PNR) 3-ZrCl [R = tBu (2a), iPr (2b)]. The molecular structures of 2a,b show that the Cu atom adopts a pseudotetrahedral coordination geometry with tripodal phosphorus moieties and a chlorine atom, whereas the ligand arrangement around the Zr atom is trigonal bipyramidal with the linear Cl-Zr-Cu axis at the apical site. A Zr-Mo heterodimetallic complex, (CO)3-Mo(Ph 2PNiPr)3ZrCl (3), is synthesized from 1b and Mo(CO) 3-(CH3CN)3, in which the ligands around the Mo center are arranged octahedrally, and three phosphorus moieties are coordinated in the fac-P3 fashion. The reaction of 1b with a square planar PtII precursor, such as (COD)PtCl2, is unique and gives (κ2-Ph2PNiPr)Pt(Ph2PNiPr) 2ZrCl3 (4), which is the first example of a Zr-Pt zwitterionic heterodimetallic complex. The reaction involves intramolecular migration of two chlorine atoms from Pt to Zr as well as that of a Ph 2PNiPr moiety from Zr to Pt.

AB - Treatment of ZrCl4 with 3 equiv. of Li(PPh2NR) (R = tBu, iPr) gives tris(phosphinoamide)zirconium complexes, (PPh 2NR)3-ZrCl [R = tBu (1a), iPr (1b)], in high yield. Crystal structures of 1a,b show that three phosphorus atoms are coordinated to the zirconium center in the solid state, whereas variable temperature NMR studies indicate a reversible coordination/dissociation process of three phosphorus atoms in the solution state. Reaction of 1a,b with CuCl give rise to the formation of Zr-Cu heterodimetallic complexes, ClCu(Ph2PNR) 3-ZrCl [R = tBu (2a), iPr (2b)]. The molecular structures of 2a,b show that the Cu atom adopts a pseudotetrahedral coordination geometry with tripodal phosphorus moieties and a chlorine atom, whereas the ligand arrangement around the Zr atom is trigonal bipyramidal with the linear Cl-Zr-Cu axis at the apical site. A Zr-Mo heterodimetallic complex, (CO)3-Mo(Ph 2PNiPr)3ZrCl (3), is synthesized from 1b and Mo(CO) 3-(CH3CN)3, in which the ligands around the Mo center are arranged octahedrally, and three phosphorus moieties are coordinated in the fac-P3 fashion. The reaction of 1b with a square planar PtII precursor, such as (COD)PtCl2, is unique and gives (κ2-Ph2PNiPr)Pt(Ph2PNiPr) 2ZrCl3 (4), which is the first example of a Zr-Pt zwitterionic heterodimetallic complex. The reaction involves intramolecular migration of two chlorine atoms from Pt to Zr as well as that of a Ph 2PNiPr moiety from Zr to Pt.

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