Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O similar to C similar to O zirconium(IV) complexes

Heuclin H; Grunstein D; Le Goff XF; Le Floch P; Mezailles N

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Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O similar to C similar to O zirconium(IV) complexes

机译：磷稳定的卡宾配合物：与O相似的C（类似于O锆（IV）配合物）的O的双膦酸酯二价阴离子的合成，反应性和DFT研究

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The reactivity of the geminal dianion of tetraisopropyl methylenediphosphonate, 3, with [ZrCl4(THF)(2)] affords a trinuclear structure 5 in which an unprecedented triscarbene-Zr dianionic fragment is found. The overall trinuclear arrangement is assembled by PO bridging moieties. The X-ray crystal structure of 5 is presented. The reaction of complex 5 with stoichiometric amounts of pyridine affords a dinuclear complex 6 whose formulation was ascertained by an X-ray crystal structure. Complexes 5 and 6 cleanly react with aldehydes (R-1)(H)C=O to afford the corresponding olefin of general formula [((OiPr)(2)P=O)(2)C=C(R-1)(H)]. DFT calculations which were carried out on the model complex of 5t and a hypothetical monometallic Zr complex [Zr(3)Cl-2(OMe2)(2)] 8t indicate that the Zr-C bond only features a weak pi-interaction between the carbon atom and a vacant orbital at the metal. The polarization of the orbital towards the carbon center is consistent with the observed nucleophilic character of the carbene complexes described here.

机译：亚甲基二膦酸四异丙酯的双键二价阴离子与[ZrCl4（THF）（2）]的反应提供了三核结构5，其中发现了前所未有的三卡宾-Zr双阴离子片段。整个三核排列是通过PO桥接部分组装而成的。给出了5的X射线晶体结构。配合物5与化学计量的吡啶的反应提供了双核配合物6，其配方由X射线晶体结构确定。配合物5和6与醛（R-1）（H）C = O干净地反应，得到相应的通式为[[（OiPr）（2）P = O）（2）C = C（R-1）的烯烃（H）]。对5t的模型络合物和假设的单金属Zr络合物[Zr（3）Cl-2（OMe2）（2）] 8t进行的DFT计算表明，Zr-C键的特征仅在于它们之间的pi相互作用弱。碳原子和金属上的空轨道。朝向碳中心的轨道极化与此处描述的卡宾配合物的亲核特征一致。

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《Dalton transactions: An international journal of inorganic chemistry》 |2010年第2期|共8页
作者
Heuclin H; Grunstein D; Le Goff XF; Le Floch P; Mezailles N;
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正文语种 eng
中图分类化学;
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CRYSTAL-STRUCTURE; RAY; DERIVATIVES; CARBONYL; CHELATE; LIGANDS; BOND;

机译：晶体结构;射线;衍生物;羰基;螯合物;脂质;键合;

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1. Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O similar to C similar to O zirconium(IV) complexes [J] . Heuclin H, Grunstein D, Le Goff XF, Dalton transactions: An international journal of inorganic chemistry . 2010,第2期

机译：磷稳定的卡宾配合物：与O相似的C（类似于O锆（IV）配合物）的O的双膦酸酯二价阴离子的合成，反应性和DFT研究
2. Synthesis, reactivity, and DFT studies of S-C-S zirconium(IV) complexes [J] . Cantat T, Ricard L, Mezailles N, Organometallics . 2006,第26期

机译：S-C-S锆（IV）配合物的合成，反应性和DFT研究
3. Investigation of the reactivity of hydroxyborate salts with group IV metal complexes: Synthesis and structural characterization of the zirconium and hafnium ionic complexes [PPN]~+[Cp_2MMe(OB(C _6F_5)_3)]~- [J] . Kelsen V., Vallée C., Jeanneau E., Organometallics . 2011,第16期

机译：羟基硼酸盐与第四族金属配合物的反应性研究：锆和ha离子配合物[PPN]〜+ [Cp_2MMe（OB（C _6F_5）_3）]〜-的合成和结构表征
4. Synthesis and structure of new bidentate bis(iV-heterocyclic carbene)-palladium complexes with xanthene framework [C] . Takeshi Makino, Ryu Yamasaki, Hyuma Masu Symposium on Organometallic Chemistry . 2008

机译：新生二泰（IV-杂环碳甲板） - Xanthene框架的合成与结构
5. Synthesis and Reactivity of Actinide Phosphorano-Stabilized Carbene and Phosphido Complexes [D] . Rungthanaphatsophon, Pokpong. 2018

机译：散氨酸磷稳定的卡宾和磷脂络合物的合成与反应性
6. Bis-N-Heterocyclic Carbene Palladium(IV) Tetrachloride Complexes: Synthesis Reactivity and Mechanisms of Direct Chlorinations and Oxidations of Organic Substrates [O] . A. Scott McCall, Hongwang Wang, John M. Desper, -1

机译：双 - N-杂环卡宾钯（IV）配合物的四氯化的合成反应性和与直接Chlorinations机制有机基质的氧化反应
7. Synthesis, Reactivity, and DFT Studies of S-C-S Zirconium(IV) Complexes [O] . -1

机译：S-C-S锆（IV）配合物的合成，反应性和DFT研究
8. Synthesis and Reactivity of Backfluorinated NHC Carbene Complexes (Briefing Charts). [R] . Blanski, R., Grubbs, R. H. 2015

机译：反氟化NHC卡宾配合物的合成和反应性（简报图）。

Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O similar to C similar to O zirconium(IV) complexes

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