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Metalated 1, 3‐Azaphospholes: η 1 ‐(1 H ‐1, 3‐Benzazaphosphole‐ P )M(CO) 5 and μ 2 ‐[(1, 3‐Benzazaphospholide‐ P )(cyclopentadienide)nickel] Complexes
Author(s) -
Heinicke Joachim,
Gupta Nidhi,
Singh Shreeyukta,
Surana Anushka,
Kühl Olaf,
Bansal Raj K.,
Karaghiosoff Konstantin,
Vogt Martin
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200213)628:13<2869::aid-zaac2869>3.0.co;2-3
Subject(s) - chemistry , phosphine , ligand (biochemistry) , crystallography , stereochemistry , crystal structure , proton nmr , catalysis , biochemistry , receptor
1 H ‐1, 3‐Benzazaphospholes react with M(CO) 5 (THF) (M = Cr, Mo, W) to give thermally and relatively air stable η 1 ‐(1 H ‐1, 3‐Benzazaphosphole‐ P )M(CO) 5 complexes. The 1 H‐ and 13 C‐NMR‐data are in accordance with the preservation of the phosphaaromatic π‐system of the ligand. The strong upfield 31 P coordination shift, particularly of the Mo and W complexes, forms a contrast to the downfield‐shifts of phosphine‐M(CO) 5 complexes and classifies benzazaphospholes as weak donor but efficient acceptor ligands. Nickelocene reacts as organometallic species with metalation of the NH‐function. The resulting ambident 1, 3‐benzazaphospholide anions prefer a μ 2 ‐coordination of the η 5 ‐CpNi‐fragment at phosphorus to coordination at nitrogen or a η 3 ‐heteroallyl‐η 5 ‐CpNi‐semisandwich structure. This is shown by characteristic NMR data and the crystal structure analysis of a η 5 ‐CpNi‐benzazaphospholide. The latter is a P‐bridging dimer with a planar Ni 2 P 2 ring and trans ‐configuration of the two planar heterocyclic phosphido ligands arranged perpendicular to the four‐membered ring.