Polymer [Pd(CH2SO2C6H4Me)(2)](n), a precursor to remarkably stable Pd organometallics

Perez-Briso Celeste; Gallego Ana M.; Martin-Alvarez Jose M.; Martinez-Ilarduya Jesus M.; Espinet Pablo

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Polymer [Pd(CH2SO2C6H4Me)(2)](n), a precursor to remarkably stable Pd organometallics

机译：聚合物[Pd（CH2SO2C6H4ME）（2）]（N），前体可显着稳定的PD Organemalirs

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A polymer [Pd(CH2SO2C6H4Me)(2)](n) is obtained by thermolysis of cis-[Pd(CH2SO2C6H4Me)(2)(NCMe)(2)] to release the MeCN ligands. The corresponding coordination sites are then occupied by weak Pd-O bonds, easier to break than the previous Pd-N bonds. This allows us to produce from the polymer cis complexes containing ligands weaker than NCMe, such as acetone or water. The complexes cis-[Pd(CH2SO2C6H4Me)(2){OC(CD3)(2)}(2)], cis-[Pd(CH2SO2C6H4Me)(2)(OH2)(2)], and cis-[Pd(CH2SO2C6H4Me)(2)(OH2) {OC(CD3)(2)}], and cyclic dimers [Pd(CH2SO2C6H4Me)(2)(OH2)](2) with bridging methylsulphone groups are formed. The Pd : PPh3 : OH2 1 : 1 : 1 reaction of the polymer produces cis-[Pd(CH2SO2C6H4Me)(2)(OH2) (PPh3)], which isomerizes to trans-[Pd(CH2SO2C6H4Me)(2)(OH2)(PPh3)], with water O-coordinated to Pd and making hydrogen bonds to the two SO2 groups as seen in its X-ray structure. A similar role is played by RNH2 groups in the structures of trans-[Pd(CH2SO2C6H4Me)(2)(NH3)(PPh3)] and the dimer mu-(N2H4) (trans-[Pd(CH2SO2C6H4Me)(2)(PPh3)])(2). In addition to these interesting intramolecular hydrogen bonding properties provided by the SO2 groups, the structural and H-1 NMR data available suggest that the CH2SO2C6H4Me group is an interesting kind of strong alkyl sigma donor, with high trans influence, and forms very stable Pd complexes extraordinarily resistant to reductive elimination and to hydrolysis by water at room temperature.

机译：通过CIS-[Pd（CH2SO2C6H4ME）（2）（NCME）（2）]热解[Pd（CH2SO2C6H4ME）（2）]（N）得到MECN配体的热解。然后通过弱PD-O键占据相应的协调位点，比以前的PD-N键更容易破裂。这允许我们从含有比NCME的配体的聚合物顺式配合物生产，例如丙酮或水。复合物顺式CIS-[Pd（CH2SO2C6H4ME）（2）{OC（CD3）（2）}（2）]，CIS-[Pd（CH2SO2C6H4ME）（2）（2）（OH2）（2）]和CIS-[PD（ CH 2 SO 2 C6H4ME）（2）（OH2）（OC 2）（OC（CD3）（2）}]和桥接甲基磺酰脲基团的环状二聚体[Pd（CH2SO2C6H4ME）（2）（2）（OH 2）]（2）。 PD：PPH3：OH2 1：1：1聚合物的反应产生顺式[Pd（CH 2 SO 2 Cl 4ME）（2）（2）（OH 2）（PPH3）]，其异构化至转型（CH 2 SO 2 Cl 6 H 4ME）（2）（2）（OH2）（PPH3）]，用水O-与Pd配位，并在其X射线结构中以两种SO2组制备氢键。转蛋白[Pd（CH2SO2C6H4ME）（2）（NH 3）（PPH3）]和二聚体MU-（N2H4）的结构中的RNH2基团播放类似的作用（转蛋白[Pd（CH2SO2C6H4ME）（2）（PPH3 ）]）（2）。除了由SO2基团提供的这些有趣的分子内氢键特性外，可提供的结构和H-1 NMR数据表明CH2SO2C6H4ME基团是一种有趣的强烷基σσ供体，具有高跨域影响，形成非常稳定的Pd络合物非常抗制性，在室温下通过水进行水解。

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来源
《Dalton transactions: An international journal of inorganic chemistry》 |2017年第25期|共8页
作者
Perez-Briso Celeste; Gallego Ana M.; Martin-Alvarez Jose M.; Martinez-Ilarduya Jesus M.; Espinet Pablo;
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Univ Valladolid Fac Ciencias IU CINQUIMA Quim Inorgan Valladolid 47071 Spain;

Univ Valladolid Fac Ciencias IU CINQUIMA Quim Inorgan Valladolid 47071 Spain;

Univ Valladolid Fac Ciencias IU CINQUIMA Quim Inorgan Valladolid 47071 Spain;

Univ Valladolid Fac Ciencias IU CINQUIMA Quim Inorgan Valladolid 47071 Spain;

Univ Valladolid Fac Ciencias IU CINQUIMA Quim Inorgan Valladolid 47071 Spain;

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正文语种 eng
中图分类化学;无机化学;
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1. Polymer [Pd(CH2SO2C6H4Me)(2)](n), a precursor to remarkably stable Pd organometallics [J] . Perez-Briso Celeste, Gallego Ana M., Martin-Alvarez Jose M., Dalton transactions: An international journal of inorganic chemistry . 2017,第25期

机译：聚合物[Pd（CH2SO2C6H4ME）（2）]（N），前体可显着稳定的PD Organemalirs
2. Preparation, spectroscopic characterization, and theoretical study of the [Pd-4(dmb)(4)(PPh3)(2)]Cl-2 complex (dmb=1,8-diisocyano-p-menthane) and its organometallic polymer {[Pd-4(dmb)(5)](CH3CO2)(2)}(n): The first examples of 58-electron linear Pd-4 [J] . Zhang TL., Harvey PD., Drouin M. Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 1999,第6期

机译：[Pd-4（dmb）（4）（PPh3）（2）] Cl-2配合物（dmb = 1,8-diisocyano-p-menthane）及其有机金属聚合物{[的制备，光谱表征和理论研究Pd-4（dmb）（5）]（CH3CO2）（2）}（n）：58电子线性Pd-4的第一个例子
3. Mixed-Ligand Organometallic Polymers Containing the "Pd_2(dmb)_2~(2+)" Fragment:Properties of the {Pd_2(dmb)_2(diphos)~(2a+)}_n Polymers/ Oligomers in Solution and in the Solid State [J] . Stephanie Sicard, Jean-Francois Berube, Dalila Samar Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2004,第17期

机译：包含“ Pd_2（dmb）_2〜（2+）”片段的混合配体有机金属聚合物：{Pd_2（dmb）_2（diphos）〜（2a +）} _ n处于溶液和固态的聚合物/低聚物的性质
4. Polymeric light-emitting diodes utilizing TPD-dispersed polyimide thin film and organometallic complex [C] . Hyuntaek Lim, Pusan National Univ., Pusan, Polymer Photonic Devices . 1998

机译：利用TPD分散的聚酰亚胺薄膜和有机金属配合物的聚合物发光二极管
5. Molecular dynamics study of diffusion of oxygen penetrates in uncrosslinked polydimethysiloxane (PDMS), crosslinked PDMS, and PDMS-based nanocomposites [D] . Ullal, Varun N. 2012

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6. Precursor-dependent structural diversity in luminescent carbonized polymer dots (CPDs): the nomenclature [O] . Qingsen Zeng, Tanglue Feng, Songyuan Tao, 2021

机译：发光碳化聚合物点（CPD）中的前体依赖性结构多样性：术语
7. Mixed-Ligand Organometallic Polymers Containing the Pd2(dmb)22+ Fragment: Properties of the {Pd2(dmb)2(diphos)2+}n Polymers/Oligomers in Solution and in the Solid State [O] . -1

机译：含有PD2（DMB）22+片段的混合配体有机金属聚合物：溶液中{PD2（DMB）2（DIBHOS）2+} N聚合物/低聚物的性质及固态
8. Polymeric Organometallics as Precursors of Polymer Supported Catalysts. [R] . Bergbreiter, D. E., Killough, J. M., Parsons, G. L. 1979

机译：聚合有机金属化合物作为聚合物负载催化剂的前体。

Polymer [Pd(CH2SO2C6H4Me)(2)](n), a precursor to remarkably stable Pd organometallics

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