Reaction of 2 or 3 equiv of potassium 1,3-bis(trimethylsilyl) with the triflate salts of Ce, Nd, Eu, Tb, and Yb gives the corresponding neutral bis-(Yb, Eu) and tris-(Ce, Nd, Tb) allyl lanthanide complexes in yields ranging from 40 to 80%. These complexes, which have been crystallographically characterized, initiate the polymerization of methyl methacrylate (MMA), but with poor turnover frequencies when compared with the corresponding salt complexes of the type K[LnA′ 3 ]. K[A′] itself initiates MMA polymerization, however, and its presence as an ion-pair in the salt complexes may contribute to the activity of heterometallic lanthanide catalysts.

A systematic study of the novel charge-transfer [(f)14-(pi)0-(f)14 --> (f)13-(pi)2-(f)13] electronic state found in 2:1 metal-to-ligand adducts of the type [(Cp)2Yb](BL)[Yb(Cp)2] [BL = tetra(2-pyridyl)pyrazine (tppz) (1), 6',6' '-bis(2-pyridyl)-2,2':4',4'':2'',2'''-quaterpyridine (qtp) (2), 1,4-di(terpyridyl)-benzene (dtb) (3), Cp = (C5Me5)] has been conducted with the aim of determining the effects of increased Yb-Yb separation on the magnetic and electronic properties of these materials. The neutral [(f)13-(pi)2-(f)13], cationic [(f)13-(pi)1-(f)13] and dicationic [(f)13-(pi)0-(f)13] states of these complexes were studied by cyclic voltammetry, UV-vis-NIR electronic absorption spectroscopy, NMR, X-ray crystallography, and magnetic susceptibility measurements. The spectroscopic and magnetic data for the neutral bimetallic complexes is consistent with an [(f)13(pi)2(f)13] ground-state electronic configuration in which each ytterbocene fragment donates one electron to give a singlet dianionic bridging ligand with two paramagnetic Yb(III) centers. The voltammetric data demonstrate that the electronic interaction in the neutral molecular wires 1-3, as manifested in the separation between successive metal reduction waves, is large compared to analogous transition metal systems. Electronic spectra for the neutral and monocationic bimetallic species are dominated by pi-pi and pi-pi transitions, masking the f-f bands that are expected to best reflect the electronic metal-metal interactions. However, these metal-localized transitions are observed when the electrons are removed from the bridging ligand via chemical oxidation to yield the dicationic species, and they suggest very little electronic interaction between metal centers in the absence of pi electrons on the bridging ligands. Analysis of the magnetic data reveals that the qtp complex displays antiferromagnetic coupling of the type Yb(alpha)(alphabeta)Yb(beta) at approximately 13 K.

Magnesium allyl complexes are regularly isolated with classical, sigma-bonded ligands, and this has been thought to be their preferred mode of bonding. Density functional theory calculations confirm that such bonding is the most stable mode when coordinated bases are present, but in their absence, pi-bonded forms are expected to be lower in energy. The isolation of the unsolvated [Mg{C(3)(SiMe(3))(2)H(3)}(2)](2) complex supports this prediction, as it is a dinuclear species in which two allyl ligands bridge the metals and display cation-pi interactions with them.

A new complex, Cp* 2Sm(tpy) ( 1, where Cp* = C 5Me 5, tpy = 2,2':6',2''-terpyridine) and its one-electron oxidized congener [Cp* 2Sm(tpy)]PF 6 ([ 1] (+)) have been synthesized and characterized with the aim of comparing their electronic and magnetic behavior to the known ytterbium analogues: Cp* 2Yb(tpy) ( 2) and [Cp* 2Yb(tpy)]OTf ([ 2] ( + )). These new samarium complexes have been characterized using single-crystal X-ray diffraction, (1)H NMR spectroscopy, cyclic voltammetry, optical spectroscopy, and bulk magnetic susceptibility measurements. All data for 1 indicate a Sm(III)-tpy* (-)[(4f) (5)-(pi*) (1)] ground-state electronic configuration similar to that found previously for 2 [(4f) (13)-(pi*) (1)]. Structural comparisons reveal that there are no significant changes in the overall geometries associated with the neutral and cationic samarium and ytterbium congeners aside from those anticipated based upon the lanthanide contraction. The redox potentials for the divalent Cp* 2Ln(THF) n precursors ( E 1/2(Sm (2+)) = -2.12 V, E 1/2(Yb (2+)) = -1.48 V) are consistent with established trends, the redox potentials (metal-based reduction and ligand-based oxidation) for 1 are nearly identical to those for 2. The correlation in the optical spectra of 1 and 2 is excellent, as expected for this ligand-radical based electronic structural assignment, but there does appear to be a red-shift ( approximately 400 cm (-1)) in all of the bands of 1 relative to those of 2 that suggests a slightly greater stabilization of the pi* level(s) in the samarium(III) complex compared to that in the ytterbium(III) complex. Similar spectroscopic overlap is observed for the monocationic complexes [ 1] (+) and [ 2] (+). Bulk magnetic susceptibility measurements for 1 reveal significantly different behavior than that of 2 due to differences in the electronic-state structure of the two metal ions. The implications of these differences in magnetic behavior are discussed.

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We report an investigation of complexes of the type M 2 (dmp) 4 (M = Mo, Cr; dmp = 2,6-dimethoxyphenyl) using resonance Raman (RR) spectroscopy, Cr isotopic substitution, and density functional theory (DFT) calculations. Assignment of the Mo-Mo stretching vibration in the Mo 2 species is straightforward as evidenced by a single resonance-enhanced band at 424 cm -1 , consistent with an essentially unmixed metal-metal stretch, and overtones of this vibration. On the other hand, the Cr 2 congener has no obvious metal-metal stretching mode near 650 -700 cm -1 , where empirical predictions based on the Cr-Cr distance as well as DFT calculations suggest that this vibration should appear if unmixed. Instead, three bands are observed at 345, 363, and 387 cm -1 that (a) have relative RR intensities that are sensitive to the Raman excitation frequency (b) exhibit overtones and combinations in the RR spectra, and (c) shift in frequency upon isotopic substitution ( 50 Cr and 54 Cr). DFT calculations are used to model the vibrational data for the Mo 2 and Cr 2 systems. Both the DFT results and empirical predictions are in good agreement with experimental observations in the Mo 2 complex but both, while mutually consistent, differ radically from experiment in the Cr 2 complex. Our experimental and theoretical results, especially the Cr isotope shifts, clearly demonstrate that the potential energy of the Cr-Cr stretching coordinate is distributed among several normal modes having both Cr-Cr and Cr-ligand character. The general significance of these results in interpreting spectroscopic observations in terms of the nature of metal-metal multiple bonding is discussed.

Unlike the parent (C3H5)4Th that decomposes at 0 degrees C, homoleptic tetra(allyl)thorium complexes [(SiMe3)nC3H5-n]4Th (n = 1, 2) have been prepared from ThBr4(thf)4 and K[(SiMe3)nC3H5-n] that are stable up to 90 degrees C (n = 1) or 124 degrees C (n = 2). The molecules, which are fluxional on the NMR time scale, contain the first structurally authenticated Th-allyl bonds. The trimethylsilyl groups cause relatively little perturbation in the core metal-allyl geometry but markedly increase the kinetic stability of the compounds.

Reaction of two equivalents of K­[1,3-(SiMe3)2C3H3] (= K­[A′]) with MnCl2 in THF produces the allyl complex A′2Mn­(thf)2; if the reaction is conducted in ether, the solvent-free heterometallic manganate species K2MnA′4 is isolated instead. With the related allyl K­[1,1′,3-(SiMe3)3C3H2] (= K­[A″]), reaction with MnCl2 in THF/TMEDA produces the corresponding adduct A″2Mn­(tmeda). In the solid state, both A′2Mn­(thf)2 and A″2Mn­(tmeda) are monomeric complexes with σ-bonded allyl ligands (Mn–C = 2.174(2) and 2.189(2) Å, respectively). In contrast, K2MnA′4 is a two-dimensional coordination polymer, in which two of the allyl ligands on the Mn cation are σ-bonded (Mn–C = 2.197(6), 2.232(7) Å) and the third is π-bonded (Mn–C = 2.342(7)–2.477(7) Å). Both σ-allyls are π-coordinated to potassium cations, promoting the polymer in two directions; the π-allyl ligand is terminal. Density functional theory (DFT) calculations indicate that isolated high-spin (C3R2H3)2Mn (R = H, SiMe3) complexes would possess π-bound ligands. A mixed hapticity (π-allyl)­(σ-allyl)­MnE structure would result with the addition of either a neutral ligand (e.g., THF, MeCN) or one that is charged (Cl, H). Both allyl ligands in a bis­(allyl)manganese complex are expected to adopt a σ-bonded mode if two THF ligands are added, as is experimentally observed in A′2Mn­(thf)2. The geometry of allyl–Mn­(II) bonding is readily modified; DFT results predict that [(C3H5)­Mn]+ and (C3H5)­MnCl should be σ-bonded, but the allyl in (C3H5)­MnH is found to exhibit a symmetrical π-bonded arrangement. Some of this behavior is reminiscent of that found in bis­(allyl)magnesium chemistry.