Syntheses, spectroscopic properties, molecular structures, and LW(NMes)(NCMe) 2b(NCMe) are reported. All complexes contain a group VI metal imido [M=NR] moiety and bonding of novel calix[4]arene imido compounds are described. Treatment of M(NtBu) 2 (NHtBu) 2 Ia (M = Mo), Ib mounted on the phenoxide rim of the calix[4]arene ligand as well as an incorporated guest molecule within the cavity. (M = W) or M(NMes) 2 Cl 2 (dme) IIa (M = Mo), IIb (M = W) (Mes = 2,4,6-Me 3 -C 6 H 2 ) with p-tBu-calix[4]arene LH 4 affords Some insights into the structures of complexes of the type LΠW(NRΠ) (LΠ = p-H-calix[4]arene; RΠ = H, Me) and into calix[4]arene metal complexes LM(NR) 1a, b (M = Mo, W; R = tBu) and 2a, b (M = Mo, W; R = Mes). Analytical and bonding in these compounds are provided by density functional theory, applying the B-P86 density functional and spectroscopic data are consistent with monomeric structures for 1 and 2, retaining a local C 4v symmetry for the an all SVP basis set within the RI-J-DFT approximation. At least one Ο bond is of importance for calix[4]arene-metal calix[4]arene metal fragment. These complexes are wellsuited to bind small molecules like acetonitrile, tBu-isonitrile, bonding in these compounds. The metal-imido bond can be described as a triple bond. A geometrically optimized or water within their macrocyclic pockets. The spectroscopic data of some inclusion compounds and the crystal structures minimum structure of LΠW(NMe) 4 shows a calix[4]arene ligand only slightly distorted from a local C 4v symmetry and of LMo(NtBu)(NCMe) 1a(NCMe), LW(NtBu)(OH 2 ) 1b(OH 2 ), LW(NtBu)(CNtBu) 1b(CNtBu), LMo(NMes)(NCMe) 2a(NCMe), an almost linear tungsten-imido moiety.
studies on metal-metal and metal-element multiple bonding [a] Institut fΓΌr Anorganische Chemie, the reaction of M(NR) 2 (OtBu) 2 with p-H-calix[4]arene
Engesserstr.,