http://www.cnr.it/ontology/cnr/individuo/prodotto/ID189365

Solution and Solid-State Dynamics of Metal-Coordinated White Phosphorus (Articolo in rivista)

Type

Prodotto della ricerca (Classe)
Articolo in rivista (Classe)

Label

Solution and Solid-State Dynamics of Metal-Coordinated White Phosphorus (Articolo in rivista) (literal)

Anno

2012-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

10.1002/chem.201201330 (literal)

Alternative label

Mirabello, Vincenzo; Caporali, Maria; Gallo, Vito; Gonsalvi, Luca; Gudat, Dietrich; Frey, Wolfgang; Ienco, Andrea; Latronico, Mario; Mastrorilli, Piero; Peruzzini, Maurizio (2012)
Solution and Solid-State Dynamics of Metal-Coordinated White Phosphorus
in Chemistry (Weinh., Print); Wiley-VCH Verlag Gmbh, Weinheim (Germania)
(literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

Mirabello, Vincenzo; Caporali, Maria; Gallo, Vito; Gonsalvi, Luca; Gudat, Dietrich; Frey, Wolfgang; Ienco, Andrea; Latronico, Mario; Mastrorilli, Piero; Peruzzini, Maurizio (literal)

Pagina inizio

11238 (literal)

Pagina fine

11250 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

18 (literal)

Rivista

Chemistry (Rivista)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo

36 (literal)

Note

ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

1. CNR, ICCOM, I-50019 Florence, Italy 2. Politecn Bari, Dipartimento Ingn Acque & Chim, I-70125 Bari, Italy 3. Univ Stuttgart, Inst Anorgan Chem, D-70569 Stuttgart, Germany 4. Univ Stuttgart, Inst Organ Chem, D-70569 Stuttgart, Germany (literal)

Titolo

Solution and Solid-State Dynamics of Metal-Coordinated White Phosphorus (literal)

Abstract

The dynamic behavior in solution of eight mono-hapto tetraphosphorus transition metal-complexes, trans-[Ru(dppm)(2)(H)(eta(1)-P-4)]BF4 ([1]BF4), trans-[Ru(dppe)(2)(H) (eta(1)-P-4)] BF4 ([2]BF4), [CpRu(PPh3)(2)(eta(1)-P-4)] PF6 ([3]PF6), [CpOs(PPh3)(2)(eta(1)-P-4)] PF6 ([4]PF6), [Cp*Ru(PPh3)(2)(eta(1)-P-4)] PF6 ([5]PF6), [Cp*Ru(dppe) (eta(1)-P-4)] PF6 ([6]PF6), [Cp*Fe(dppe) (eta(1)-P-4)] PF6 ([7]PF6), [(triphos) Re(CO)(2)(eta(1)-P-4)] OTf ([8]OTf), and of three bimetallic Ru(mu,eta(1:2)-P-4)Pt species [{Ru-(dppm)(2)(H)}(mu,eta(1:2)-P-4){Pt(PPh3)(2)}]BF4 ([1-Pt]BF4), [{Ru(dppe)(2)(H)}(mu,eta(1:2)-P-4){Pt(PPh3)(2)}]BF4 ([2-Pt] BF4), [{CpRu (PPh3)(2))}(mu,eta(1:2)-P-4){Pt(PPh3)(2)}]BF4 ([3-Pt]BF4), [dppm=bis(diphenylphosphanyl) methane; dppe=1,2-bis(diphenylphosphanyl) ethane; triphos=1,1,1-tris (diphenylphosphanylmethyl)ethane; Cp=eta(5)-C5H5; Cp*=eta(5)-C5Me5] was studied by variable-temperature (VT) NMR and P-31{H-1} exchange spectroscopy (EXSY). For most of the mononuclear species, NMR spectroscopy allowed to ascertain that the metal-coordinated P-4 molecule experiences a dynamic process consisting, apart from the free rotation about the M-P-4 axis, in a tumbling movement of the P-4 cage while remaining chemically coordinated to the central metal. EXSY and VT 31P NMR experiments showed that also the binuclear complex cations [1-Pt](+) -[3-Pt](+) are subjected to molecular motions featured by the shift of each metal from one P to an adjacent one of the P-4 moiety. The relative mobility of the metal fragments (Ru vs. Pt) was found to depend on the co-ligands of the binuclear complexes. For complexes [2]BF4 and [3]PF6, MAS, P-31 NMR experiments revealed that the dynamic processes observed in solution (i.e., rotation and tumbling) may take place also in the solid state. The activation parameters for the dynamic processes of complexes 1(+), 2(+), 3(+), 4(+), 6(+), 8(+) in solution, as well as the X-ray structures of 2(+), 3(+), 5(+), 6(+) are also reported. The data collected suggest that metal-coordinated P-4 should not be considered as a static ligand in solution and in the solid state. (literal)

Editore