2016 **Abstract:** In the presence of thf or tmeda and depending on experimental conditions, 1-phenylcyclopropyllithium may be crystallised as either dinuclear or tetranuclear species both exhibiting α-CC agostic distortions towards tricoordinate lithium cations. In thf solution, deaggregation of the dinuclear complex takes place to yield a well-defined mononuclear species [Li(thf)3(c-CPhC2H4)].

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(9 citation statements)

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“…As observed for 2, [16] this non-symmetric situation is accompanied by a marked a-CC agostic distortion of the cyclopropyl group A with Li1. Indeed, the structure of 3 presents a conspicuously acute LiÀCaÀCb angle [Li1ÀC1ÀC2 79.47(13)8 vs. Li2ÀC1ÀC3 114.62(13)8] together with a short Li···Cb distance [Li1···C2 2.392(4) ] and an elongated Ca À Cb bond [C1 À C2 1.561(2) vs. C1 À C3 1.524 (2) ].…”

confidence: 61%

“…As observed for 2, [16] this non-symmetric situation is accompanied by a marked a-CC agostic distortion of the cyclopropyl group A with Li1. Indeed, the structure of 3 presents a conspicuously acute LiÀCaÀCb angle [Li1ÀC1ÀC2 79.47(13)8 vs. Li2ÀC1ÀC3 114.62(13)8] together with a short Li···Cb distance [Li1···C2 2.392(4) ] and an elongated Ca À Cb bond [C1 À C2 1.561(2) vs. C1 À C3 1.524 (2) ].…”

confidence: 61%

“…Up to now there are only two examples of tetramers crystallizing as squares, unknown for unsupported Li + (Scheme 1, below): 1) a benzyllithium derivative, where the lithium cations are coordinated to a bidentate O,N-donor base in [{m-CH 2 Ph}Li-{k 2 -Me 2 N(CH 2 ) 2 OMe}] 4 , [14] and 2) an aryllithium derivative, 2,4,6-tri(isopropyl)phenyllithium in which lithium-p-arene interactions complement the Li À C s-bonds. [15] Capitalizing on previous work on [Li(thf) 2 (m-c-CPhC 2 H 4 ) 2 Li(thf)], [16] we now report that seemingly weaker secondary interactions in the form of CC agostic interactions may support Lewis basefree two-coordinate lithium cations in cyclopropyl derivatives arranged as a square in [{m-c-C(SiMe 3 )C 2 H 4 }Li] 4 .…”

supporting

confidence: 59%

“…Up to now there are only two examples of tetramers crystallizing as squares, unknown for unsupported Li + (Scheme , below): 1) a benzyllithium derivative, where the lithium cations are coordinated to a bidentate O,N‐donor base in [{μ‐CH 2 Ph}Li{κ 2 ‐Me 2 N(CH 2 ) 2 OMe}] 4 , and 2) an aryllithium derivative, 2,4,6‐tri(isopropyl)phenyllithium in which lithium‐π‐arene interactions complement the Li−C σ‐bonds . Capitalizing on previous work on [Li(thf) 2 (μ‐ c ‐CPhC 2 H 4 ) 2 Li(thf)], we now report that seemingly weaker secondary interactions in the form of CC agostic interactions may support Lewis base‐free two‐coordinate lithium cations in cyclopropyl derivatives arranged as a square in [{μ‐ c ‐C(SiMe 3 )C 2 H 4 }Li] 4 .…”

confidence: 99%

“…Quantum chemical calculations are valuable tools to elucidate the agostic and π-interactions between the s-block metal ions and multiple bonds [25,26]. Isoelectronic ion pairs such as Na + /Mg 2+ , K + /Ca 2+ /Sc 3+ , Rb + /Sr 2+ /Y 3+ , and Cs + /Ba 2+ /La 3+ allow one to deduce the influence of electronegativity, size and hardness on reactivity and bonding parameters.…”

confidence: 99%