Premium
Acyl‐Functionalized Molybdenum Compounds [(η 3 ‐C 3 H 5 )(η 5 ‐Cp′)Mo(CO) 2 ]: An Experimental Study Including the X‐ray Structure of a Rare endo Conformer
Author(s) -
Schejbal Jiří,
Honzíček Jan,
Vinklárek Jaromír,
Erben Milan,
Růžičková Zdeňka
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402700
Subject(s) - chemistry , reactivity (psychology) , molybdenum , crystal structure , cyclopentadienyl complex , protonation , crystallography , stereochemistry , medicinal chemistry , group 2 organometallic chemistry , x ray crystallography , molecule , catalysis , inorganic chemistry , organic chemistry , medicine , ion , alternative medicine , pathology , physics , diffraction , optics
A series of new acyl‐functionalized molybdenum(II) complexes [(η 3 ‐C 3 H 5 )(η 5 ‐C 5 H 4 COR)Mo(CO) 2 ] have been successfully synthesized and crystallographically characterized, and the relationship between the reactivity and electronic properties of these organometallic compounds has been studied in detail. The X‐ray analysis revealed [(η 3 ‐C 3 H 5 )(η 5 ‐C 5 H 4 COCF 3 )Mo(CO) 2 ] to exist as a rare endo conformer, the first time that this structure has been observed in the crystal lattice of a [(η 3 ‐C 3 H 5 )(η 5 ‐Cp′)Mo(CO) 2 ] (Cp′ = substituted Cp) complex without any disorder. It has also been demonstrated that the derivatives bearing very strong electron‐withdrawing acyl groups (e.g., ‐CHO, ‐COCF 3 ) show different outcomes in the protonation reactions compared with the parent cyclopentadienyl compound or derivatives bearing less electron‐withdrawing groups (e.g., ‐COMe, ‐COPh). This study has also revealed the increased reactivity of the formyl derivative [(η 3 ‐C 3 H 5 )(η 5 ‐C 5 H 4 CHO)Mo(CO) 2 ] towards aromatic amines. An IR spectroscopic analysis revealed that the aldimine‐functionalized products formed very quickly even under the mild conditions that fulfill the basic rules of click chemistry.