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Metallinduzierte und basenkatalysierte 2‐Propinyl‐Allenyl‐Umlagerung in [(HCCCH 2 )(2,4,6‐ t Bu 3 C 6 H 2 O)]PMoCP(CO) 2
Author(s) -
Leise Michael,
Lang Heinrich,
Imhof Wolfgang,
Zsolnai Laszlo
Publication year - 1993
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19931260503
Subject(s) - chemistry , propynyl , reactivity (psychology) , medicinal chemistry , ligand (biochemistry) , stereochemistry , double bond , metal , polymer chemistry , receptor , organic chemistry , medicine , biochemistry , alternative medicine , pathology
Metal‐Induced and Base‐Catalyzed 2‐Propynyl‐Allenyl Rearrangement in [(HCCCH 2 )(2,4,6‐ t Bu 3 C 6 H 2 O)]PMoCP(CO) 2 The synthesis and reactivity of [(HCCCH 2 )(2,4,6‐ t Bu 3 1‐C 6 H 2 O)]PMoCp(CO) 2 ( 3 ) is described. [(HCCCH 2 )(R)]PCl ( 1 ) reacts with NaMoCp(CO) 3 ( 2 ) to afford the s̀ 3 ,λ 4 1‐phosphanediyl compounds 3 . With NEt 3 a prototropic rearrangement of the 2‐propynyl ligand of 3 to an allenyl group in [(H 2 CCCH)(R)]PMoCp(CO) 2 ( 5 ) is observed. However, with Cr(CO) 5 · THF a metal‐induced rearrangement of the 2‐propynyl unit in 3 yields η 3 ‐{(2,4,6‐ t Bu 3 C 6 H 2 O)[(CO) 5 Cr]PCHCCH 2 }MoCp(CO) 2 ( 7 ). Complex 7 contains a 1‐phosphaallyl system, which is functionalized by an exocyclic CC double bond X‐ray structure analyses of 3 and 7 are performed.