A combination of phase-transfer and traditional alkylation strategies has been employed to synthesise sterically encumbered 1,3-di(cyclohexyl) and 1,3-di(tert-butyl) substituted indenes in multi-gram quantities. These indenyl ligands and sterically demanding alkyl cyclopentadienyl ligands have been used to prepare a series of [(η(7)-C(7)H(7))Zr(η(5)-L)] (L = Cp and Ind) complexes by straightforward salt metathesis between [(η(7)-C(7)H(7))ZrCl(tmeda)] and the corresponding sodium indenide or cyclopentadienide. All of these Zr complexes have been characterized by elemental analysis, NMR spectroscopy and single crystal X-ray diffraction. The structural information derived from these studies was employed to evaluate the steric demand of these ligands in a realistic manner.

The reaction of the cycloheptatrienylzirconium half-sandwich complex [(η(7)-C(7)H(7))ZrCl(tmeda)] (1) (tmeda = N,N,N',N'-tetramethylethylenediamine) with Li(Im(Dipp)N), generated from bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) with methyllithium, yields the imidazolin-2-iminato complex [(η(7)-C(7)H(7))Zr(Im(Dipp)N)(tmeda)] (2). The corresponding tmeda-free complex [(η(7)-C(7)H(7))Zr(Im(Dipp)N)] (5) can be synthesized via the 1,3-bis(trimethylsilyl)allyl complex [(η(7)-C(7)H(7))Zr{η(3)-C(3)H(3)(TMS)(2)}(THF)] (3; TMS = SiMe(3)), which undergoes an acid-base reaction with Im(Dipp)NH to form 5 and 1,3-bis(trimethylsilyl)propene. 5 exhibits an unusual one-legged piano stool ("pogo stick") geometry with a particularly short Zr-N bond of 1.997(2) Å. Addition of 2,6-dimethylphenyl or tert-butyl isocyanide affords the complexes [(η(7)-C(7)H(7))Zr(Im(Dipp)N)(CNR)] (R = o-Xy, 6; R = t-Bu, 7), while the reaction with 2,6-dimethylphenyl isocyanate results in a [2 + 2] cycloaddition to form the ureato(1-) complex [(η(7)-C(7)H(7))Zr{Im(Dipp)N(C═O)N-o-Xy}] (8). 5 can also act as an initiator for the ring-opening polymerization of ε-caprolactone. These reactivity patterns together with density functional theory calculations reveal a marked similarity of the bonding in imidazolin-2-iminato and conventional imido transition-metal complexes.

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This tutorial review summarizes the organometallic chemistry derived from the half-sandwich complex [(η(7)-C(7)H(7))ZrCl(tmeda)], which was used as an efficient and versatile starting material for the incorporation of monoanionic ligands into the cycloheptatrienyl zirconium coordination sphere by conventional salt metathesis reactions. A broad variety of ligands was employed, affording novel and previously inaccessible cycloheptatrienyl (sandwich) complexes of the type [(η(7)-C(7)H(7))Zr(Y)]; Y comprises pentadienyl, cyclopentadienyl, allyl, phospholyl, boratabenzene, imidazolin-2-iminato and amido systems. The cycloheptatrienyl ring in these systems usually acts as an "innocent spectator ligand", but reactivity can arise from the second ligand Y or the Lewis acidity of the, formally, Zr(+iv) center, which was probed in selected examples and put in perspective to related studies. The corresponding results emphasize why the use of [(η(7)-C(7)H(7))ZrCl(tmeda)] is clearly an advancement in the chemistry of the still fairly unexplored area of cycloheptatrienyl transition metal complexes.

The reactions of Zr(C 7 H 7 )(Cl)(tmeda) (tmeda = tetramethylethylenediamine) with pentadienyl anions lead to formally tetravalent Zr(C 7 H 7 )(Pdl) complexes, for Pdl = C 5 H 7 , 2,4-C 7 H 11 , 6,6-dmch, and c-C 7 H 9 (C 7 H 11 = dimethylpentadienyl, dmch = dimethylcyclohexadienyl, c-C 7 H 9 = cycloheptadienyl). Structural characterizations of the first three have been carried out, revealing much shorter Zr-C distances for the C 7 H 7 ligand and a pattern of Zr-C bond distances for the pentadienyl ligands that is consistent with a formally high (þ4) metal oxidation state, which is also supported by DFT calculations. As had been found for the analogous Cp complexes, these 16-electron species are susceptible to Lewis base coordination, and the 2,6-xylyl isocyanide adducts of the 2,4-C 7 H 11 and 6,6-dmch complexes have been isolated and characterized by IR spectroscopy and single-crystal X-ray diffraction studies. The IR spectroscopic studies indicate that the pentadienyl ligands are serving as better net electron donors than Cp ligands, opposite what is typically found for related but lower valent species. At high temperatures the 16-electron Zr(C 7 H 7 )(C 5 H 7 ) complex undergoes slow conversion to the corresponding Cp complex.

The indenyl effect has been introduced to pentadienyl ("open cyclopentadienyl") chemistry by preparation of the phenylmethallyl ("open indenyl") ligand oInd(Me). The reaction of its potassium salt K(oInd(Me)) with [(η(5)-C(5)Me(5))RuCl](4) afforded the sandwich complex [(η(5)-C(5)Me(5))Ru(η(5)-oInd(Me))] (1), which, upon treatment with PMe(3), CO, and 2,6-dimethylphenyl isocyanide (CN-o-Xy), easily underwent η(5)-η(3) hapticity interconversion and formed the complexes [(η(5)-C(5)Me(5))Ru(η(3)-oInd(Me))(L)] (2, L = PMe(3); 3, L = CO; 4, L = CN-o-Xy). In these complexes, the η(3)-bound phenylmethallyl ligand adopts an anti-conformation with regard to the relative positions of the phenyl and methyl substituents. For the PMe(3) complex anti-2, slow conversion to the syn-isomer was observed, and this equilibrium reaction was monitored by NMR spectroscopy at 50 °C to determine a first order rate constant of k(323 K) = 6.57 × 10(-6) (± 0.02 × 10(-6)) s(-1) and an activation barrier of ΔG° = 26.8 kcal mol(-1). DFT calculations afforded a stabilization of syn-2 and syn-3 by ΔG(298) = -1.54 and -1.74 kcal mol(-1) over the respective anti-isomer.

The reactions of Zr(C7H7)(Cl)(tmeda) (tmeda = N,N,N′,N′-tetramethylethylene-1,2-diamine) with cyclopentadienyl and substituted cyclopentadienyl anions have led to the expected Zr(C7H7)(C5H4R) and Zr(C7H7)(C9H7) complexes (R = H, CH3, SiMe3, C3H5 (allyl), PPh2; C9H7 = indenyl). The R = H and PPh2 complexes had previously been reported, but their preparations were accompanied by lower yields, among other drawbacks. The approach reported herein thus appears to offer a fairly general, effective, and convenient method for the preparation of zirconium complexes containing the C7H7 and a variety of monoanionic ligands. Structural data have been obtained for the R = CH3, SiMe3, and allyl species, as well as the indenyl complex. These data are consistent with previous conclusions that the zirconium center is present in a formal +4 oxidation state. Despite the 16-electron configurations for these species, the R = allyl complex showed no coordination of this substituent. As an apparent result of the hard nature of Zr(IV), weak THF coordination to the R = SiMe3 complex was observed to take place, via a structural study. Structural data were also obtained for the previously characterized Zr(C7H7)(C5H5){CN[2,6-C6H3(CH3)2]} complex.

An improved synthesis of 2,5-di(tert-butyl)-3,4-dimethylpyrrole (2-H, HPyr(tBu(2)Me(2))) and a subsequent reaction with KH yield K(Pyr(tBu(2)Me(2))) (2-K) in multi-gram quantities. Four different pyrrolyl (Pyr) and imidazolyl (Im) ligands were used in salt metathesis reactions with [(η(7)-C(7)H(7))ZrCl(tmeda)] (7) to afford a series of azatrozircenes: [(η(7)-C(7)H(7))Zr(η(5)-Pyr(tBu(2)))] (1-Zr), [(η(7)-C(7)H(7))Zr(η(5)-Pyr(tBu(2)Me(2)))] (2-Zr), [(η(7)-C(7)H(7))Zr(η(5)-Pyr(tBu(3)))] (3-Zr) and [(η(7)-C(7)H(7))Zr(η(5)-Im(tBu(3)))] (4-Zr), which were characterized by NMR spectroscopy and elemental analysis. In addition, the molecular structures of 2-H, 2-K·18-crown-6, 1-Zr, 2-Zr and 4-Zr were determined by X-ray diffraction analysis, revealing η(5)- rather than κ(1)-N-coordination of the N-heterocyclic ligands. Cone angle measurements on the sandwich complexes 1-Zr–4-Zr showed that their nitrogencontaining ligands belong to the class of very sterically encumbered π-ligands, but DFT calculations suggest lower stabilities compared to their all-carbon analogues.