In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2003, No. 21 ( 2003-11), p. 3958-3967
Kurzfassung:
The binuclear platinum( II ) hydride [Pt 2 (dcype) 2 (H) 3 ][Cl] ( 1b ) has been isolated in high yields by treatment of Pt(dcype)Cl 2 with NaBH 4 (molar ratio 1:2) in ethanol solution at room temperature. This one‐pot synthesis is not straightforward when starting from diphenylphosphanylalkane complexes. The compounds [Pt 2 (dppp) 2 (H) 3 ][OH] ( 3b ) and [Pt 2 (dppb) 2 (H) 3 ][OH] ( 4 ) were isolated by starting from the mononuclear hydrides { cis ‐[Pt(P‐P)(H) 2 ]} while mixtures of both binuclear {[Pt 2 (dppe) 2 (H) 3 ] + , 5 } and trinuclear {[Pt 3 (dppe) 3 (H) 3 ] + , 6 } trihydrides were obtained with the dppe ligand. Various salts of the cation 1 , [Pt 2 (dcype) 2 (H) 3 ][X] (X = BF 4 , 1a ; OH, 1c ; BPh 4 , 1d ), were isolated either from [Pt(dcype)(μ‐OH)] 2 [BF 4 ] 2 ( 2 ) by a general procedure ( 1a ), or by decomposition of the complex cis ‐[Pt(dcype)(H) 2 ] in solution ( 1c ), as well as by metathesis reactions ( 1a , 1c , and 1d ). Compounds 1a , 1b , and 1d react with CO under mild conditions to afford the corresponding Pt I binuclear hydrides [Pt 2 (dcype) 2 (μ‐CO)(μ‐H)][X] (X = Cl, 7a ; BF 4 , 7b ; BPh 4 , 7c ). The binuclear core of cation 1 is broken by KCN in methanol solution, yielding the mononuclear complex cis ‐[Pt(dcype)(CN)(H)] ( 8 ). The complexes 1a − d , 2 , 7a − c , and 8 have been characterised by FAB MS, IR, and NMR ( 1 H, 31 P, and 195 Pt) spectroscopic techniques; the 1 and 7 cations show fluxional behaviour on the NMR timescale. The structure of compound 1d was determined, at 200 K, by single‐crystal X‐ray diffraction. All the hydrido ligands were located. The Pt−Pt separation is 2.696(1) Å and the coordination geometry around each platinum centre can be regarded as distorted square planar. Incoherent Inelastic Neutron Scattering (INS) spectra were obtained for 1a and [Pt 2 (dppe) 2 (H) 3 ][BF 4 ] ( 5a ); the spectra reflect the different geometries of the two “P 4 Pt 2 (H) 3 ” cores as found by single‐crystal structure determinations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Materialart:
Online-Ressource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2003:21
DOI:
10.1002/ejic.200300252
Sprache:
Englisch
Verlag:
Wiley
Publikationsdatum:
2003
ZDB Id:
1475009-0
