A sandwich complex of lithium oxide: {Li[BunC(NBut)2]}4·Li2O

Chivers, Tristram; Downard, Andrew; Yap, Glenn P. A.

doi:10.1039/a804955f

Cited by 41 publications

(23 citation statements)

References 15 publications

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“…In this case, other, less hindered laddering units must be employed to promote secondary laddering. For example, the aggregation of 4 with Li 2 O in a non‐coordinating solvent yields the cluster [Li{( n Bu)C(N t Bu) 2 }] 4 ·Li 2 O ( 5 ) 16. In 5 , two Li[( n Bu)C(N t Bu) 2 ] monomers associate laterally to give a homomolecular, dimeric PLU.…”

Section: Two‐stage Laddering In Lithium Heterocarboxylatesmentioning

confidence: 99%

Applications of the Laddering Principle — A Two-Stage Approach to Describe Lithium Heterocarboxylates

Downard

Chivers

2001

Eur. J. Inorg. Chem.

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Since the development of the laddering principle in the mid‐1980s, it has become a useful concept for describing structural features in a wide variety of organoalkali metal (particularly organolithium) and other main‐group element oligomers. Here a brief account of the laddering principle is given, and a two‐stage approach to understanding structural diversity is described for several lithium heterocarboxylates. “Primary laddering” describes the initial aggregation of monomeric units, whereas “secondary laddering” deals with the assembly of these primary laddered units into larger structures. Both homo‐ and heteromolecular clusters can be formed by these processes. In this context, several examples are discussed, with particular emphasis on the effects of solvation and heteroatoms.

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Section: Two‐stage Laddering In Lithium Heterocarboxylatesmentioning

confidence: 99%

Applications of the Laddering Principle — A Two-Stage Approach to Describe Lithium Heterocarboxylates

Downard

Chivers

2001

Eur. J. Inorg. Chem.

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“…The result is that the Li 2 O moiety can be viewed as being sandwiched between two twisted Li 2 (N 2 C) 2 ladders. 4 This symmetry is, however, not retained in benzene solution, where 7 Li NMR spectroscopy reveals two signals and thus points to a higher average symmetry (D 2 ) species.…”

Section: Metal Organo-and Inorganooxidesmentioning

confidence: 99%

“…Specifically, in the case of organolithium species, it has been noted that both LiOH and (more commonly) Li 2 O can form co-complexes with unreacted organometallic, LiR. 4 It is worth pointing out that it is not uncommon to describe lithium oxide-containing clusters as cocomplexes of the type (LiR) n •Li 2 O. However, as the subsequent discussion will show, designation of the Li 2 O fragment is almost always arbitrary for symmetry reasons.…”

Section: Moisturementioning

confidence: 99%

“…29 These results point to the elimination of isobutene from ME(O t Bu) 4 to give ME(O t Bu) 3 OH with the hydroxy group then acting as an oxide source in the formation of 40-42 [eqn. (4)]. The problem of crystallographic disordering of the metal centres noted above for 38 and 39 recurs in pseudo-octahedral 42, but is solved rather ingeniously by its treatment with THF to give (THF) 4 •K 4 Sb 2 (O t Bu) 8 (O) 43 [eqn.…”

Section: Metal Oxidesmentioning

confidence: 99%

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The oxygen scavenging properties of alkali metal-containing organometallic compounds

Wheatley

2001

Chem. Soc. Rev.

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“…Recently, the focus of amidinate research has swayed from the dinuclear transition metal species of the preceding decades toward Group 13 metal catalytic studies popularised,12–14 amongst others, by Jordan et al15–17 To compliment these, the amidinate chemistries of Groups 2 and 1418–42 have also received attention in an effort to exploit an untapped research area. In stark contrast, the study of Group 1 amidinate chemistry, particularly formamidinate, has remained scarce 8, 43–50. The groups of both Lappert51–59 and Arnold60–64 have done most to address this by advancing the chemistry of benzamidinates and guanidinates (R 2 =NR 2 ).…”

Section: Introductionmentioning

confidence: 99%

Structural Studies of N,N′‐Di(ortho‐fluorophenyl)formamidine Group 1 Metallation

Cole

Evans

Junk

et al. 2003

Chemistry A European J

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The treatment of N,N'-di(ortho-fluorophenyl)formamidine (HFPhF) in tetrahydrofuran with equimolar amounts of n-butyllithium, sodium bis(trimethylsilyl)amide or potassium bis(trimethylsilyl)amide affords the colourless crystalline formamidinate complexes [Li(FPhF)(thf)] (1), [Na(FPhF)(thf)] (2) and [K(FPhF)] (5). Low-temperature preparation of 2 in diethyl ether yields the Et(2)O adduct [Na(FPhF)(Et(2)O)] (3). At ambient temperature the sodium fluoride inclusion complex [Na(3)(FPhF)(3)(Et(2)O)(NaF)] (4) is also formed. Spectroscopic ((1)H, (13)C and (19)F((1)H) NMR) data for 1-5, microanalytical analyses for compounds 1, 2 and 5 and X-ray structure determinations for 1, 3-5 confirm the formulae of these species. In the solid-state, 1 and 3 possess a dimeric nature in which the formamidinate ligands coordinate through mu(2):eta(2):eta(1) (1) and mu(2):eta(2):eta(2) (3) binding modes. These are enabled by partial ortho-fluoro donation. Compound 4, which is also dimeric, contains two trisodium tris(formamidinate) units that comprise mu(2):eta(2):eta(2)-FPhF ligands, a bridging diethyl ether moiety and an unprecedented mu(3):eta(2):eta(2):eta(2)-formamidinate donor. Together, these trinuclear units encapsulate two sodium fluoride units by eta(2)-N,N-formamidinate chelation of the sodium cations (thereby creating further mu(3):eta(2):eta(2):eta(2)-bound formamidinates) and fluoride-sodium interactions. Compound 5 extends the coordinative versatility of FPhF to mu(2):eta(4):eta(3) coordination by the generation of K(2)(mu(2):eta(4):eta(3)-FPhF)(2) units that exhibit eta(2)-arene interactions. Macromolecularly, the overlaying of these units affords a polymeric solvent-free structure that incites coordination of the FPhF ligands to metal atoms above and below the K(2)(FPhF)(2) plane. Overall, this generates a remarkable mu(4):eta(4):eta(3):eta(2):eta(1)-amidinate binding mode that incorporates both bridging and terminal fluorine donors. Compounds 1-5 are the first non-chromium complexes of N,N'-di(ortho-fluorophenyl)formamidinate.

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A sandwich complex of lithium oxide: {Li[BunC(NBut)2]}4·Li2O

Cited by 41 publications

References 15 publications

Applications of the Laddering Principle — A Two-Stage Approach to Describe Lithium Heterocarboxylates

Applications of the Laddering Principle — A Two-Stage Approach to Describe Lithium Heterocarboxylates

The oxygen scavenging properties of alkali metal-containing organometallic compounds

Structural Studies of N,N′‐Di(ortho‐fluorophenyl)formamidine Group 1 Metallation

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