OsXCl（PPh）（X=H,Cl）与炔丙基氯反应合成烯基卡拜配合物及膦配体调控的锇-氢卡拜向卡宾配合物的转化

简单的锇起始物OsHCl（PPh）（1）或OsCl（PPh）（2）与3-氯-3-甲基-1-丁炔反应可分别得到锇的烯基卡拜配合物OsHCl（≡CCH=CMe）（PPh）（3）和OsCl（≡CCH=CMe）（PPh）（4）.化合物3与二苯基（苯乙炔基）膦反应可转化为三个二苯基（苯乙炔基）膦配位的锇烯基卡宾配合物OsCl（=CHCH=CMe）（PhPC≡CPh）（5）,而化合物4与二苯基（苯乙炔基）膦反应得到膦配体取代产物OsCl（≡CCH=CMe）（PhPC≡CPh）（6）.二苯基（苯乙炔基）膦配体较弱的供电子能力及较小的空间位阻是促成化合物3发生锇上的原子氢配体到卡拜碳的1,2-迁移而转化为卡宾配合物5的原因.国家重点基础研究发展计划(973计划,No.2012CB821600)；国家自然科学基金(No.21072161)资助项目~~

Alkenylcarbyne Complexes Derived from the Reactions of OsXCl-(PPh3)(3) (X=H, Cl) with Propargyl Chloride and Phosphine Ligand-Controlled Transformation of Hydride-Carbyne to Carbene

简单的锇起始物OsHCl(PPh_3)_3(1)或OsCl_2(PPh_3)_3(2)与3-氯-3-甲基-1-丁炔反应可分别得到锇的烯基卡拜配合; 物OsHCl_2(=CCH=CMe_2)(PPh_3)_2(3)和OsCl_3(=CCH=CMe_2)(PPh_3)_2(4).化合物3与二苯基; (苯乙炔基)膦反应可转化为三个二苯基(苯乙炔基)膦配位的锇烯基卡宾配合物OsCl_2(=CHCH=CMe_2)(Ph_2PC=CPh)_3(5); ,而化合物4与二苯基(苯乙炔基)膦反应得到膦配体取代产物OsCl_3(=CCH=CMe_2)(Ph_2PC=CPh)_2(6).二苯基(苯乙炔基; )膦配体较弱的供电子能力及较小的空间位阻是促成化合物3发生锇上的原子氢配体到卡拜碳的1,2-迁移而转化为卡宾配合物5的原因.Reactions of the simple osmium precursors OsHCl(PPh3)(3) (1) or OsCl2(PPh3)(3) (2) with 3-chloro-3-methylbut-1-yne afforded OsHCl2( CCH=CMe2)(PPh3)(2) (3) or OsCl3( CCH=CMe2)(PPh3)(2) (4), respectively. Treatment of 3 with Ph2PC CPh led to alp formation of the tris-diphenyl(phenylethynyl)phosphine alkenylcarbene complex OsCl2(=CHCH=CMe2)(Ph2PC CPh)(3) (5), while complex 4 underwent simple phosphine ligand substitution with Ph2PC CPh to give OsCl3( CCH=CMe2)(Ph2PC-CPh)(2) (6). Presumably, upon the phosphine ligand substitution of PPh3 in 3 by Ph2PC CPh, the relatively electron -poor nature of the later decreased the electron density of the osmium center, and thus promoted the transformation of the hydride-carbyne to carbene via the 1,2 -shift of the hydride ligand from Os to the carbyne carbon, which was then further facilitated by the coordination of a third less bulky Ph2PC-CPh ligand to the osmium center to give the stable 18e product 5.National Basic Research Prpgram of China (973 Program) [2012CB821600];; National Natural Science Foundation of China [21072161

Dichlorido(η4-cyclo­octa-1,5-diene)bis­(triphenyl­phosphine)osmium(II)

The OsII atom in the title compound, [OsCl2(C8H12)(C18H15P)2], is located on a crystallographic twofold axis and adopts a distorted octa­hedral coordination geometry. The two triphenyl­phosphine ligands are trans to each other, while the two chlorine ligands are cis-disposed. The coordination is completed by the cyclo­octa­diene (COD) ligand with bonding to the two olefin double bonds. The C=C bond has a length of 1.403 (6) Å, which is significntly longer than a free olefinic double bond (≃1.34 Å)

钌亚丙二烯基配合物与肼的反应性质:丙烯腈配合物的生成（英文）

以双齿P,N-配体8-（二苯基膦基）喹啉（DPPQ）为支撑配体的钌亚丙二烯基配合物[RuCl（=C=C=CR2）（DPPQ）2]-[BPh4]（3a:R=苯基;3b:CR2=FN=亚芴基）可由双核钌配合物[Ru（μ-Cl）（DPPQ）2]2[BPh4]2（1）分别与过量的1,1-二苯基炔丙醇（2a）或9-乙炔-9-芴醇（2b）反应得到.配合物3易与肼在室温下反应生成丙烯腈的钌配合物[RuCl（N≡C—CH=CR）2)（DPPQ）)2][BPh)4]（4a:R=苯基;4b:CR）2=FN=亚芴基),该反应涉及肼对亚丙二烯基配体α-碳原子的分子间亲核进攻,是首例肼对金属亚丙二烯基加成生成丙烯腈的反应.配合物4与过量的丙炔醇2反应可释放出3,3-二苯基丙烯腈（5a）或3-芴基丙烯腈（5b）,并再生亚丙二烯基配合物3.此外,初步考察了配合物1对端基炔丙醇与肼反应生成丙烯腈的催化活性,结果表明该催化反应的确可以进行,但是得到的丙烯腈产物的产率不高.尽管结果不是很理想,但是这些研究表明可望发展端基炔丙醇与肼经由过渡金属亚丙二烯基中间体转化为丙烯腈的新催化反应.Project supported by the National Basic Research Program of China(973 Program,No.2012CB821600);;the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT_17R65)~

Synthesis and Organometallic Properties of Several Osmium Alkenylcarbyne Complexes

OSH2Cl2(PCy3)2(1)与炔丙醇HC≡CC(OH)PH2在室温及加热条件下反应可分别生成原子氢配位的γ-羟基卡拜配合物OSHCl2[≡CCH2C(OH)PH2](PCy3)2(2)和原子氢配位的烯基卡拜OSHCl2(≡CCH=CPH2)(PCy3)2(3).2和3在氯化氢乙醚溶液作用下可转化为三氯配位的烯基卡拜OSCl3(≡CCH=CPH2)(PCy3)2(4).也可通过OSH2Cl2(PCy3)2与HC≡CC(OH)PH2在氯化氢乙醚溶液存在下反应,由一锅法直接合成烯基卡拜配合物4.化合物4还可通过OSCl3(≡CCH=CPH2)(PPH3)2(5)与PCy3的配体取代反应来制备,在反应过程中可分离到单个PPH3配体被PCy3取代的产物OSCl3(≡CCH=CPH2)(PCy3)(PPH3)(6).化合物4可与水及吡啶发生配体取代反应,分别生成水或吡啶配位的单膦卡拜配合物OSCl3(≡CCH=CPH2)(PCy3)(S)(S=H2O,7;S=Py,8).此外,4与nAOET在室温下反应可得到锇烯基卡宾配合物OSCl2(=CHCH=CPH2)(PCy3)2(9),而与ETOH需在加热条件下才可反应,生成的是原子氢卡拜3.化合物9在溶液中不稳定,可完全转化为热力学稳定的原子氢配位的卡拜3.Reactions of the dihydride complex OsH2Cl2(PCy3)2(1) with HC≡CC(OH)Ph2at room temperature or under heating condition produce the hydride hydroxycarbyne complex OsHCl2[≡CCH2C(OH)Ph2](PCy3)2(2) and the hydride alkenylcarbyne complex OsHCl2(≡CCH=CPh2)(PCy3)2(3), respectively.Treatment of 2 or 3 with HCl Et2O affords the trichlorocarbyne complex OsCl3(≡CCH=CPh2)(PCy3)2(4), which can be conveniently synthesized by the one pot reaction of 1with HC≡CC(OH)Ph2in the presence of HCl Et2O.Complex 4 can be alternatively prepared from the phosphine ligand substitution of the trichlorocarbyne complex OsCl3(≡CCH=CPh2)(PPh3)2(5) with PCy3, from which the mono-substituted intermediate OsCl3(≡CCH=CPh2)(PCy3)(PPh3)(6) can be isolated.Complex 4 undergoes ligand substitution reactions with water and pyridine leading to the formation of the aqua and pyridine-coordinate mono phosphine carbyne complexes OsCl3(≡CCH=CPh2)(PCy3)(S)(S=H2O, 7; S=Py, 8).In addition, complex 4 reacts with NaOEt at room temperature to produce the alkenylcarbene complex OsCl2(=CHCH=CPh2)(PCy3)2(9), which is unstable in solution and evolves into the thermally more stable hydride carbyne complex 3.In contrast, the reaction of 4 with EtOH can only take place at elevated temperature to give the hydride carbyne 3.国家自然科学基金(No.21072161); 国家重点基础研究发展计划(973计划;No.2012CB821600); 长江学者和创新团队发展计划资助项目~

Tris(2-sulfidopyridine N-oxide-O,S)chromium(III) acetone solvate (1/1)

The title compound, [Cr(C5H4NOS)(3)].(CH3)(2)CO, contains a Cr-III(mpo)(3) unit (Hmpo = 2-mercaptopyridine N-oxide) and (CH3)(2)CO. Each mpo(-) ligand chelates to the Cr atom via one O and one S atom with an average bite angle of 83.3(1)degrees, forming a distorted octahedral O3S3 coordination environment of the Cr atom. The average Cr-S and Cr-O bond distances are 2.363(1) and 1.986(2) Angstrom, respectively

Synthesis and characterization of a bimetallic iridium complex with a ten sp(2)-carbon chain bridge

A special sp(2)-carbon chain bridged bimetallic iridium complex has been synthesized and characterized; the compound has excellent air-stability, thermo-stability and electrochemical properties

Stabilization of anti-aromatic and strained five-membered rings with a transition metal

1981年诺贝尔化学奖获得者、美国康奈尔大学RoaldHoffmann教授评价该项工作说：'The　paper is an excellent one--it's　quite a mazing that the parent Os　system,molecule 1,chooses to give the osmapentalyne'。德国化学家Uwe Rosenthal教授等在同期《自然—化学》杂志的《News and Views》栏目以《Breaking the rules》为题撰文评述了这一研究成果。全文地址：http://www.nature.com/nchem/journal/vaop/ncurrent/pdf/nchem.1702.pdfAnti-aromatic compounds, as well as small cyclic alkynes or carbynes, are particularly challenging synthetic goals. The combination of their destabilizing features hinders attempts to prepare molecules such as pentalyne, an 8π-electron anti-aromatic bicycle with extremely high ring strain. Here we describe the facile synthesis of osmapentalyne derivatives that are thermally viable, despite containing the smallest angles observed so far at a carbyne carbon. The compounds are characterized using X-ray crystallography, and their computed energies and magnetic properties reveal aromatic character. Hence, the incorporation of the osmium centre not only reduces the ring strain of the parent pentalyne, but also converts its Hückel anti-aromaticity into Craig-type Möbius aromaticity in the metallapentalynes. The concept of aromaticity is thus extended to five-membered rings containing a metal–carbon triple bond. Moreover, these metal–aromatic compounds exhibit unusual optical effects such as near-infrared photoluminescence with particularly large Stokes shifts, long lifetimes and aggregation enhancement

Vanadium chemistry of o-mercaptophenol Part IV Construction of heterobinuclear complexes via the synthon V(mp)(3) (2-) (mp = o-mercaptophenolato dianion) Syntheses and structures of (BzMe(3)N)(2) V(mp)(3) center dot MeCN center dot 1/2 MeOH and V-Co c

The mononuclear complex (BzMe(3)N)(2)[V(mp)(3)] . MeCN . 1/2 MeOH (1) (mp = o-SC6H4O2-) obtained by reacting VCl3 with Na(2)mp in the presence of BzMe(3)NBr contains the synthon [V(mp)(3)](2-). Further reaction with Co-2(CO)(8) gave [V(mp)(3)Co(Py)(2)(MeCN)] . 2MeCN (2) and [V(mp)(3)Co(DMF)(3)] (3), depending on the recrystallization conditions. The coordination geometry of the V atoms in all these complexes lies between an octahedron and a trigonal prism. Upon formation of (2) and (3), the terminal oxo atoms of mp become mu(2)-O bridges between V and Co, while the latter atom is also octahedral

Chiral phosphine ligands derived from sugars 14 Crystal structure of diphenyl(methyl 4 ‘,6 ‘-O-benzylidene-3 ‘-deoxy-alpha-D-altropyranoside-3-) phosphine oxide

The crystal structure of the title compound, C26H27O6P, has been determined by single-crystal X-ray diffraction analysis. The crystal is orthorhombic with space group P2(1)2(1)2(1), a = 6. 154 (4), b = 17. 199 (8), c = 22. 180 (3) Angstrom, V = 2347. 6 Angstrom(3), D-c = 1. 32 g/cm(3), F(000) = 984, mu = 1. 5 cm(-1), Z = 4, and final R = 0. 075 and R-w = 0. 080 for 1417 reflections (I greater than or equal to 3 sigma(I)). The X-ray diffraction analysis revealed that the structure of the title compound s similar to that of its parent phosphine and the pyranose and 4, 6-O-benzylidene rings remain distorted chair conformations