Indenylidene

The Ru -C(,(indenylidene) bond distances are significantly shorter than the bond length between the ruthenium and the weaker tt-acid imidazol-2-ylidene (1.852(3) A vs 2.102(3) A in 26 and 1.861(4) A vs 2.113(4) A in 28). Selected bond lengths and bond angles for 25 and 27 are presented in Tables VII and VIII, respectively. 

It has been possible to record the IR and UV spectra of several derivatives of the carbene [75] - tetrachlorocyclopentadienylidene [80], indenylidene [81] and fluorenylidene [82] (Bell and Dunkin, 1985). These carbenes were formed by UV photolysis of the corresponding diazo precursors frozen in inert matrices and have a triplet ground state. The carbenes [80]-[82] react with CO in inert matrices at 30 K, but exhibit a lower reactivity than the carbene [75]. Furthermore, they were stabilized in a pure CO matrix at 12 K, whereas the free carbene [75] could not be detected under these conditions. The different reactivity towards CO between [75] and [80]-[82] may be associated with the different steric shielding of the carbene centres and with the different triplet-singlet gap as well. 

Fig. 3.28 ROMP initiators, first, second and third generation Grubbs catalysts (complexes 71, 72, and 73, respectively) 74a-c 3-phenyl-indenylidene replaces the benzylidene carbene...

For a thorough review of Ru-NHC-catalysts for metathesis, see Samojlowicz C, Bieniek M, Grela K (2009) Chem Rev 109 3708-3742 for ruthenium indenylidene-complexes in cross metathesis, see Boeda F, Bantreil X, Clavier H, Nolan SP (2008) Adv Synth Catal 350 2959-2966 For Hll-types systems, see Schrodi Y, Pederson RL (2007) Aldrichimica Acta 40 45-52... 

The matrix photochemistry of 2n24 and 2o92 is completely analogous to that of 2a. The primary irreversible loss of nitrogen from 2 produces carbenes 1 in photostationary equilibria with cyclopropenes 3 (Scheme 15). The relative amounts of 1 and 3 formed in the matrix depends very much on the wavelength used for the irradiation. Both carbenes In and lo were chemically identified by oxygen trapping. UV irradiation (248 nm) of In produces a mixture of indeneketene 21, CO, and indenylidene 22 (Scheme 14). 

Fluorenylidene and Indenylidene Dications Insights about Antiaromaticity... 

The results from studies on fluorenylidene dications such as 8 demonstrate clearly that species of this type are antiaromatic. However, extension of these studies to indenylidene dications such as 13 has important advantages. The... 

We have not yet prepared the unsubstituted indenylidene fluorene dication 17 but the NICSO) (18) values demonstrate that the fluorenyl cation is still more antiaromatic than the indenyl cation, see Table III. 

To perform a similar evaluation for the indenyl cation, 18, we must examine the bis-indenylidene dication, 19, and the appropriate data for both systems is given in Table IV. While 19 is more antiaromatic than 18 by all measures, the dependence of the measure of aromaticity and presumably antiaromaticity on ring size requires that the values for 19 be divided by 2. When examined in this manner, the indenyl cation 18 is more antiaromatic than 19, in contrast to the behavior of the fluorenyl system in 7 and 3. 

We have demonstrated that oxidation of fluorenylidenes and indenylidenes results in the formation of dications with appreciable antiaromaticity. The antiaromaticity of these species was examined for a series of dications from... 

The antiaromaticity of indenyl cations was examined in the dications of indenylidene fluorenes. Contrary to expectation, the fluorenyl cation was more antiaromatic than the indenyl cation in these systems. The sum of NICS(l)zz values was linearly related to global measures of antiaromaticity such as A, suggesting that they could be used to evaluate antiaromaticity in a local sense, for individual rings. 

Scheme 15 Acid-promoted allenylidene to indenylidene rearrangement...

Although the chemistry of pentatetraenylidene complexes [M]=C(=C)3=CR R has not received as much attention as that of aUenylidenes, there is ample experimental evidence to confirm the electrophilic character of the C, Cy and carbons of the cumulenic chain [26-29, 31]. Thus, treatment of tra s-[RuCl(=C=C=C=C=CPh2) (dppe)2][PFg] (132) with alcohols or secondary amines resulted in addition of the nucleophilic solvent across the Cy=Cs double bond to give alkenyl-allenylidenes 138 (Scheme 48) [358]. In chloroform, electrophilic cyclization with one of the Ph groups occurred to give 139. This transformation is actually the parent of the later observed allenylidene to indenylidene intramolecular rearrangement (Scheme 15). 

Ru]= [RuCI(Ti6-p-cymene)(PR3)] PR3= PCys, P/Pr3, PPh3 Scheme 2.4 Acid-promoted allenylidene to indenylidene rearrangement. 

An unusual intramolecular addition of one ortho C-H bond of a phenyl substituent across the C3=C4 bond in 20 (Scheme 3.33) is observed on thermolysis of 20 in CHCI3 [7]. A similar complex is also formed when the corresponding dppm complex is generated in situ from [Cl(dppm)2Ru-C = C-C = C-C(Ph)20SiMe3] and HBF4 in CH2CI2 [30, 31]. This transformation is actually the parent of the later commonly observed allenylidene to indenylidene intramolecular rearrangement. 

Ruthenium Allenylidenes and Indenylidenes as Catalysts in Alkene Metathesis... 

Among the R2C(=C) =Ru homologs promoting alkene metathesis the most recent discoveries deal vhth the allenylidene-ruthenium and related pre-catalysts. This chapter is devoted to the class of ruthenium-allenylidene metathesis precatalysts, their intramolecularly rearranged indenylidene catalysts, and their use in... 

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