FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2155174311> ?p ?o ?g. }

• W2155174311 endingPage "5934" @default.
• W2155174311 startingPage "5918" @default.
• W2155174311 abstract "Reactions of HC(Me2pz)3 with Grignard reagents, dialkyl magnesium compounds and dimethylzinc are reported, together with a DFT study on some of the aspects of this chemistry. Reactions of HC(Me2pz)3 with MeMgX (X=Cl or Br) gave the half-sandwich zwitterionic compounds [Mg(MeTpmd)X] (X=Cl (2) or Br (3); MeTpmd−=[C(Me2pz)3]−). Addition of HCl to 2 gave the structurally characterised half-sandwich compound [Mg{HC(Me2pz)3}Cl2(thf)] (4). The zwitterionic sandwich compound [Mg(MeTpmd)2] (5) formed in low yields in the reaction of MeMgX with HC(Me2pz)3 but was readily prepared from HC(Me2pz)3 and either MgnBu2 or MgPh2. The structurally characterised compound 5 contains two “naked” sp3-hybridised carbanions fully separated from the dicationic metal centre. Only by using MgPh2 as starting material could the half-sandwich compound [Mg(MeTpmd)Ph(thf)] (6) be isolated. The zwitterionic sandwich compound 5 reacted with HOTf (OTf−=[O3SCF3]−) to form the dication [Mg{HC(Me2pz)3}2]2+ (72+), which was structurally characterised. Pulsed field gradient spin-echo (PGSE) diffusion NMR spectroscopy revealed both compounds to be intact in solution. In contrast to the magnesium counterparts, HC(Me2pz)3 reacted only slowly with ZnMe2 (and not at all with ZnPh2) to form the half-sandwich zwitterion [Zn(MeTpmd)Me] (8), which contains a cationic methylzinc moiety separated from a single sp3-hybridised carbanion. Density functional calculations on the zwitterions [M(MeTpmd)Me] and [M(MeTpmd)2] (M=Mg, Zn) revealed that the HOMO in each case is a MeTpmd-based carbanion lone pair. The κ1C isomers of [M(MeTpmd)Me] were calculated to be considerably less stable than their κ3N-bound counterparts, with the largest gain in energy for Mg due to the greater ease of electron transfer from metal to the MeTpmd apical carbon atom on formation of the zwitterion. Moreover, the computed MC bond dissociation enthalpies of the κ1C isomers of [M(MeTpmd)Me] are considerably higher than expected by simple extrapolation from the corresponding computed HC bond dissociation enthalpy." @default.
• W2155174311 created "2016-06-24" @default.
• W2155174311 creator A5013590724 @default.
• W2155174311 creator A5035371569 @default.
• W2155174311 creator A5037065857 @default.
• W2155174311 creator A5079306493 @default.
• W2155174311 creator A5080000742 @default.
• W2155174311 creator A5082334085 @default.
• W2155174311 creator A5091794897 @default.
• W2155174311 date "2008-06-27" @default.
• W2155174311 modified "2023-09-29" @default.
• W2155174311 title "Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions" @default.
• W2155174311 cites W1498162837 @default.
• W2155174311 cites W1635658086 @default.
• W2155174311 cites W1862070135 @default.
• W2155174311 cites W1953032341 @default.
• W2155174311 cites W1963683620 @default.
• W2155174311 cites W1963900422 @default.
• W2155174311 cites W1964120198 @default.
• W2155174311 cites W1964699153 @default.
• W2155174311 cites W1966100675 @default.
• W2155174311 cites W1966290469 @default.
• W2155174311 cites W1966410544 @default.
• W2155174311 cites W1966716482 @default.
• W2155174311 cites W1968970485 @default.
• W2155174311 cites W1969989728 @default.
• W2155174311 cites W1970416350 @default.
• W2155174311 cites W1972438903 @default.
• W2155174311 cites W1972868152 @default.
• W2155174311 cites W1974349103 @default.
• W2155174311 cites W1976818535 @default.
• W2155174311 cites W1977172349 @default.
• W2155174311 cites W1978017364 @default.
• W2155174311 cites W1978526800 @default.
• W2155174311 cites W1978876839 @default.
• W2155174311 cites W1979112822 @default.
• W2155174311 cites W1980830800 @default.
• W2155174311 cites W1981828560 @default.
• W2155174311 cites W1981875114 @default.
• W2155174311 cites W1981938342 @default.
• W2155174311 cites W1982721890 @default.
• W2155174311 cites W1984456478 @default.
• W2155174311 cites W1984530362 @default.
• W2155174311 cites W1985143312 @default.
• W2155174311 cites W1985361327 @default.
• W2155174311 cites W1986086085 @default.
• W2155174311 cites W1986820754 @default.
• W2155174311 cites W1987206449 @default.
• W2155174311 cites W1988091937 @default.
• W2155174311 cites W1988284720 @default.
• W2155174311 cites W1989360530 @default.
• W2155174311 cites W1989392022 @default.
• W2155174311 cites W1989412279 @default.
• W2155174311 cites W1991292133 @default.
• W2155174311 cites W1992162389 @default.
• W2155174311 cites W1992180947 @default.
• W2155174311 cites W1992238540 @default.
• W2155174311 cites W1992498741 @default.
• W2155174311 cites W1992567078 @default.
• W2155174311 cites W1993105393 @default.
• W2155174311 cites W1993327079 @default.
• W2155174311 cites W1993383767 @default.
• W2155174311 cites W1993544311 @default.
• W2155174311 cites W1994358660 @default.
• W2155174311 cites W1994972096 @default.
• W2155174311 cites W1995640619 @default.
• W2155174311 cites W1995962029 @default.
• W2155174311 cites W1996778213 @default.
• W2155174311 cites W1998563836 @default.
• W2155174311 cites W1998750102 @default.
• W2155174311 cites W1999158508 @default.
• W2155174311 cites W2001145902 @default.
• W2155174311 cites W2001208751 @default.
• W2155174311 cites W2002717616 @default.
• W2155174311 cites W2003391538 @default.
• W2155174311 cites W2003609201 @default.
• W2155174311 cites W2004804700 @default.
• W2155174311 cites W2005692644 @default.
• W2155174311 cites W2005719582 @default.
• W2155174311 cites W2009209190 @default.
• W2155174311 cites W2010824029 @default.
• W2155174311 cites W2011076790 @default.
• W2155174311 cites W2014361505 @default.
• W2155174311 cites W2018116767 @default.
• W2155174311 cites W2018313475 @default.
• W2155174311 cites W2018399161 @default.
• W2155174311 cites W2019529889 @default.
• W2155174311 cites W2022716519 @default.
• W2155174311 cites W2022737477 @default.
• W2155174311 cites W2023757288 @default.
• W2155174311 cites W2024843155 @default.
• W2155174311 cites W2026643405 @default.
• W2155174311 cites W2027153834 @default.
• W2155174311 cites W2028022118 @default.
• W2155174311 cites W2028386566 @default.
• W2155174311 cites W2028506102 @default.
• W2155174311 cites W2028639007 @default.
• W2155174311 cites W2029243263 @default.

• next