In:
Zeitschrift für anorganische und allgemeine Chemie, Wiley, Vol. 635, No. 9-10 ( 2009-07), p. 1362-1366
Abstract:
The reaction of the azaphospholes 5‐methyl‐2‐phenyl‐1,2,3‐diazaphospole (PDAP) and 2‐methyl‐2‐phenyl‐1,2,4,3‐triazaphospole (PTAP) with the dimers [LMCl 2 ] 2 (LM = η 6 ‐C 6 Me 6 Ru, η 5 ‐C 5 Me 5 Ir) of ruthenium(II) and iridium(III) only occurs in presence of nucleophiles such as EtOH or H 2 O leading to their metal‐coordination after cleavage of the dimers. [( η 6 ‐C 6 Me 6 )RuCl 2 ] 2 reacts with PDAP and EtOH in the molar ratio 0.5:1:1 to give the phosphorus‐coordinated complex ( η 6 ‐C 6 Me 6 )RuCl 2 ( P ‐PDAP · EtOH) ( 1 ). In the case of [( η 5 ‐C 5 Me 5 )IrCl 2 ] 2 , the triazaphosphole PTAP was used in the presence of EtOH or H 2 O yielding the analogous products ( η 5 ‐C 5 Me 5 )IrCl 2 ( P ‐PTAP · EtOH) ( 2 ) or ( η 5 ‐C 5 Me 5 )IrCl 2 ( P ‐PTAP · H 2 O) ( 3 ). In 1 – 3, the former aromatic azaphosphole ( σ 2 , λ 3 ‐P) has been converted by 1,2 addition of EtOH or H 2 O to their P=C or P=N double bond with the nucleophiles EtO – and OH – bonded to phosphorus ( σ 3 , λ 3 ‐P). Complexes 1 – 3 with a piano‐stool configuration were characterized by elemental analysis, 31 P NMR spectroscopy and single‐crystal X‐ray diffraction.
Type of Medium:
Online Resource
ISSN:
0044-2313
,
1521-3749
DOI:
10.1002/zaac.v635:9/10
DOI:
10.1002/zaac.200900240
Language:
English
Publisher:
Wiley
Publication Date:
2009
detail.hit.zdb_id:
201094-X
detail.hit.zdb_id:
1481139-X
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