Synthesis, structure, and reactivity of a stabilized calcium carbene: R(2)CCa.
Attempted 2-fold deprotonation of the bis(iminophosphorano)methane ligand, H(2)C(Ph(2)P=NSiMe(3))(2) (4-H(2)), with a calcium amide led only to mono-deprotonation. The crystal structure of (4-H)(2)Ca shows two tridentate ligands with short Ca-N and a rather long Ca-C bond. Reaction of 4-H(2) with a dibenzylcalcium complex gave the desired 2-fold deprotonation and formation of 4-Ca, which crystallized as a dimeric complex. Analysis of the calculated atomic and group charges in 4-H(2), (4-H)(2)Ca, and [4-Ca](2) showed that the negative charge at the imine nitrogens only slightly increases upon successive deprotonation of 4-H(2). The electron density at the central carbon, however, increases considerably: the charge on the carbene carbon in [4-Ca](2) is ca. -1.8. The negative charge in 4(2)(-) is therefore mainly located on the carbon. Reaction of [4-Ca](2) with benzophenone in benzene gave the remarkably stable adduct [4-Ca](2) x O=CPh(2), which was characterized by X-ray diffraction. Reaction of [4-Ca](2) with adamantylcyanide gave exclusive formation of the adduct [4-Ca](2) x (N identical withCR)(2), which did not react further, even at higher temperatures. Addition of cyclohexyl isocyanate to a benzene solution of [4-Ca](2) gave immediate [2 + 2]-cycloaddition and formation of a dianionic tetradentate ligand that binds to Ca(2+) through two nitrogens, the central carbon, and an oxygen. This product crystallized as a dimer with bridging oxygen atoms.
Orzechowski
Lars
L
Department of Chemistry, University Duisburg-Essen, Universitätsstrasse 5-7, 45117 Essen, Germany.
Jansen
Georg
G
Harder
Sjoerd
S