Reactivity of the zwitterionic ligand EtNHC(S) Ph2P=NPPh2C(S)NEt towards [Ru-3(CO)(12)]. Sulfur transfer and ligand fragmentation leading to the methideylamide[-N(Et)-CH(R)-] mu(3)-bridging moiety

Delferro M; Pattacini R; Cauzzi D; Graiff C; Terenghi M; Predieri G; Tiripicchio A

首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Reactivity of the zwitterionic ligand EtNHC(S) Ph2P=NPPh2C(S)NEt towards [Ru-3(CO)(12)]. Sulfur transfer and ligand fragmentation leading to the methideylamide[-N(Et)-CH(R)-] mu(3)-bridging moiety

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Reactivity of the zwitterionic ligand EtNHC(S) Ph2P=NPPh2C(S)NEt towards [Ru-3(CO)(12)]. Sulfur transfer and ligand fragmentation leading to the methideylamide[-N(Et)-CH(R)-] mu(3)-bridging moiety

机译：两性离子配体EtNHC（S）Ph2P = NPPh2C（S）NEt对[Ru-3（CO）（12）]的反应性。硫转移和配体断裂导致甲叉酰胺[-N（Et）-CH（R）-] mu（3）-桥连部分

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The reaction of EtNHC(S)Ph2P=NP+Ph2C(S)N-Et (HEtSNS) with [Ru-3(CO)(12)] has been carried out under two different experimental conditions: in the first case [Ru-3(CO)(12)], previously turned into the labile intermediate [Ru-3(CO)(10)(CH3CN)(2)], afforded, at room temperature in dichloromethane, the trinuclear clusters [Ru-3(CO)(11)(CNEt)] (1), {Ru-3(CO)(9)(mu-H)[(mu-S: kappa-P) Ph2PN= PPh2C(S) NEt]} (2), {Ru-3(CO)(9)(mu-H)[(mu-S: kappa-P) Ph2PN= P(S) Ph-2]} (3) and {Ru-3(CO)(10)[(mu-kappa P-2)Ph2PNHPPh2]} (4). Ligand fragmentation occurs via loss of EtNC or EtNCS, without sulfur transfer to the cluster core. In the second case, [Ru-3(CO)(12)] reacted with HEtSNS in toluene at 70 degrees C, giving the trinuclear clusters 4, {Ru-3(CO)(7)(CNEt)(mu(3)-S)[(mu(2)-N: eta(1)-C: kappa(1)-P) Ph2PN= PPh2C(H) NEt]} (5), {Ru-3(CO)(8))(mu(3)-S)[(mu(2)-N:eta-C: kappa-P) Ph2PN= PPh2C(H) NEt]} (6) and {Ru-3(CO)(6)(mu(3)- CO)(mu(3)-S)(EtNC)[(mu-k(2)P) Ph2PNHPPh2]} (7). The last three compounds derive from ligand fragmentation and sulfur transfer to the metal cluster. All compounds were characterized by spectroscopy (NMR, IR) and the molecular structures of 2, 5 and 7 were determined by single-crystal X-ray diffraction. Cluster 2 preserves the original Ru-3 triangular core in which an edge is bridged by a hydride ligand and by the sulfur atom of the Ph2PN= PPh2C(S) NEt ligand. Cluster 5 shows an open triangle of Ru atoms capped by a mu(3)-sulfide and by the unprecedented methideylamide -N(Et)CH(R)-mu(3)-bridging moiety of the Ph2PN= PPh2C(H) NEt ligand. It formally derives from cluster 6 by substitution of ethyl isonitrile with one CO molecule. Finally, cluster 7 displays a Ru-3(mu(3)-S)(mu(3)-CO) trigonal bipyramidal core.

机译：EtNHC（S）Ph2P = NP + Ph2C（S）N-Et（HEtSNS）与[Ru-3（CO）（12）]的反应是在两种不同的实验条件下进行的：第一种情况是[Ru- 3（CO）（12）]，以前变成不稳定的中间体[Ru-3（CO）（10）（CH3CN）（2）]，在室温下于二氯甲烷中提供三核簇[Ru-3（CO））（11）（CNEt）]（1），{Ru-3（CO）（9）（mu-H）[（mu-S：kappa-P）Ph2PN = PPh2C（S）NEt]}（2）， {Ru-3（CO）（9）（mu-H）[（mu-S：kappa-P）Ph2PN = P（S）Ph-2]}（3）和{Ru-3（CO）（10） [（μ-κ-2）Ph2PNHPPh2]}（4）。配体碎裂是通过EtNC或EtNCS的丢失而发生的，而没有硫转移到簇芯。在第二种情况下，[Ru-3（CO）（12）]与HEtSNS在甲苯中于70℃反应，得到三核簇4，{Ru-3（CO）（7）（CNEt）（mu（3） -S）[（mu（2）-N：eta（1）-C：kappa（1）-P）Ph2PN = PPh2C（H）NEt]}（5），{Ru-3（CO）（8））（mu（3）-S）[（mu（2）-N：eta-C：kappa-P）Ph2PN = PPh2C（H）NEt]}（6）和{Ru-3（CO）（6）（mu （3）-CO）（mu（3）-S）（EtNC）[（mu-k（2）P）Ph2PNHPPh2]}（7）。最后三种化合物来自配体断裂和硫转移至金属簇。所有化合物均通过光谱法（NMR，IR）表征，并通过单晶X射线衍射确定2、5和7的分子结构。簇2保留了原始的Ru-3三角形核，其边缘由氢化物配体和Ph2PN = PPh2C（S）NEt配体的硫原子桥接。簇5显示了由mu（3）-硫化物和Ph2PN = PPh2C（H）NEt配体的前所未有的甲叉酰胺-N（Et）CH（R）-mu（3）桥接部分覆盖的Ru原子的开放三角形。它通过用一个CO分子取代乙基异腈而正式从簇6衍生而来。最后，簇7显示了Ru-3（mu（3）-S）（mu（3）-CO）三角双锥核。

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《Dalton transactions: An international journal of inorganic chemistry》 |2009年第3期|共6页
作者
Delferro M; Pattacini R; Cauzzi D; Graiff C; Terenghi M; Predieri G; Tiripicchio A;
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正文语种 eng
中图分类无机化学;
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CARBONYL CLUSTER COMPOUNDS; CRYSTAL-STRUCTURE; MOLECULAR-STRUCTURE; NIDO-CLUSTERS; STRUCTURAL CHARACTERIZATIONS; ELECTROCHEMICAL-BEHAVIOR; MAIN GROUP; COMPLEXES; RUTHENIUM; SULFIDO;

机译：碳簇化合物;晶体结构;分子结构;中性簇;结构特征;电化学行为;主要基团;化合物;钌;硫代基;

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1. Reactivity of the zwitterionic ligand EtNHC(S) Ph2P=NPPh2C(S)NEt towards [Ru-3(CO)(12)]. Sulfur transfer and ligand fragmentation leading to the methideylamide[-N(Et)-CH(R)-] mu(3)-bridging moiety [J] . Delferro M, Pattacini R, Cauzzi D, Dalton transactions: An international journal of inorganic chemistry . 2009,第3期

机译：两性离子配体EtNHC（S）Ph2P = NPPh2C（S）NEt对[Ru-3（CO）（12）]的反应性。硫转移和配体断裂导致甲叉酰胺[-N（Et）-CH（R）-] mu（3）-桥连部分
2. A study on the coordinative versatility of the zwitterionic S,N,S ligand EtNHC(S)Ph2P = NPPh2C(S)NEt in its anionic, neutral and cationic forms - Determination of absolute pK(a) values in CH2Cl2 of Rh-I complexes [J] . Delferro M, Cauzzi D, Pattacini R, European journal of inorganic chemistry . 2008,第14期

机译：两性离子S，N，S配体EtNHC（S）Ph2P = NPPh2C（S）NEt的阴离子，中性和阳离子形式的配合通用性的研究-Rh-I配合物CH2Cl2中绝对pK（a）值的测定
3. A study on the coordinative versatility of the zwitterionic S,N,S ligand EtNHC(S)Ph2P = NPPh2C(S)NEt in its anionic, neutral and cationic forms - Determination of absolute pK(a) values in CH2Cl2 of Rh-I complexes [J] . Delferro M, Cauzzi D, Pattacini R, European journal of inorganic chemistry . 2008,第14期

机译：两性离子S，N，S配体EtNHC（S）Ph2P = NPPh2C（S）NEt的阴离子，中性和阳离子形式的配合通用性的研究-Rh-I配合物CH2Cl2中绝对pK（a）值的测定
4. EPR Studies and Ferromagnetic Interaction of a Dinuclear Copper Complex Mediated by mu-1,1 Bridging Azido Group of the Ligand Hsalamp [C] . R. Srinivasan, B. Natarajan, R. Venkatesan Asia-Pacific EPR/ESR Symposium . 2006

机译：通过MU-1,1桥接氮杂铜铜介导的二核铜复合物的EPR研究和铁磁性相互作用的配体Hsalamp
5. Mechanisms of electron transfer and hydrogen activation in selected triruthenium clusters with multiple bridging ligands. Part I. The attenuation of radical reactivity in triruthenium trihydrido(alkylidyne) clusters. Electrochemistry and kinetics of decomposition of the 47-electron cluster radical, via a disproportionation path. Part II. The activation of molecular hydrogen at transition metal centers via kinetics and mechanism of reversible oxidative addition of hydrogen across the metal-metal bond of (mu-hydrogen)(2)Ruthenium(3)(Carbon monoxide)(8)(mu-phosphorus(t-BU)(2))(2). [D] . Bierdeman, David John. 2000

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6. Sulfur Donor Atom Effects on Copper(I)/O2 Chemistry with Thioanisole Containing Tetradentate N3S Ligand Leading to μ-12-Peroxo-Dicopper(II) species [O] . Yunho Lee, Dong-Heon Lee, Ga Young Park, -1

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7. Role of the Ligand and of the Size and Flexibility of the Palladium-Ancillary Ligand Cycle on the Reactivity of Substituted Alkynes toward Palladium(0) Complexes Bearing Potentially Terdentate Nitrogen-Sulfur-Nitrogen or Nitrogen-Nitrogen-Nitrogen Ligands: Kinetic and Structural Study [O] . -1

机译：钯 - 辅助配体循环对钯（0）复合物的取代炔烃反应性的作用和柔韧性，其具有潜在幸滞氮硫 - 氮气或氮氮 - 氮配体的钯（0）络合物：动力学和结构研究
8. Chemistry of Polynuclear Metal Complexes with Bridging Carbene or Carbyne Ligands. Part 90. (1) Synthesis of the Complexes (W2M2(mu-CO)(mu-CMe)(mu3-CMe)-(Mu-PPh2)2(CO)3(eta-C5H5)2) (M = Rh or Ir) and Related Tetra- and Penta-nuclear Metal Compounds: Interconversion of Ketenyl and Lambda(5) -Phospha-alkyne Ligands Bridging Tungsten-Rhodium Bonds. [R] . Davies, S. J., Stone, F. G. 1989

机译：具有桥接卡宾或卡宾配体的多核金属配合物的化学。部分90.（1）配合物的合成（W2m2（mu-CO）（mu-Cme）（mu3-Cme） - （mu-pph2）2（CO）3（eta-C5H5）2）（m = Rh或Ir）和相关的四核和五核金属化合物：Ketenyl和Lambda（5）-phospha-alkyne配体桥联钨 - 铑键的相互转化。

Reactivity of the zwitterionic ligand EtNHC(S) Ph2P=NPPh2C(S)NEt towards [Ru-3(CO)(12)]. Sulfur transfer and ligand fragmentation leading to the methideylamide[-N(Et)-CH(R)-] mu(3)-bridging moiety

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