具有膦-吡啶杂配体o -Ph 2 PC 6 H 4 CH 2 O(CH 2)n C 5 H 4 N-2(n = 1-3)的方形钯(II)配合物的合成,表征和结构。具有反螯合双齿PN配体的第一个过渡金属配合物的分离
摘要:
钠的反应2 [的PdCl 4 ]或[的PdCl 2(PHCN)2 ]与具有P和能够A N施主原子新的二齿配位体的混合等摩尔量的反式螯合,ö -Ph 2 PC 6 H ^ 4 CH 2 O(CH 2)n C 5 H 4 N-2(n = 1-3),主要产生1:1的配合物[PdCl 2 { o -Ph 2 PC 6 H 4 CH 2 O(CH 2)nC 5 H 4 N-2}]。根据连接膦基和吡啶基的主链的长度,主要形成顺式或反式配位的配合物。当n= 1时,形成顺式配合物1,但是具有较长桥的配体分别给出反式配合物2和3作为主要产物。由钯(II)配合物与邻-Ph 2 PC 6 H 4 CH 2 O(CH 2)n C反应生成5 H 4 N-2( n = 2或3)三核配合物[Pd 3 Cl 6 { o -Ph 2 PC 6 H 4 CH 2 O-(CH 2) n C 5 H 4 N-2} 2 ] 4( n
Preferential Geometry and Reactivity of Neutral Iridium(III) and Rhodium(III) Complexes Bearing a Flexible Heterochelate PN Ligand (PN = <i>o</i>-Ph<sub>2</sub>PC<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>OCH<sub>2</sub>C<sub>5</sub>H<sub>4</sub>N-2)
rhodium(III) complexes coordinated to the metal center in a facial manner. A ligand exchange reaction of the PPh3 iridium(III) complex 1a with PCy3 did not proceed well (20% conversion), while a similar reaction of the PPh3 rhodium(III) complex 4a with PCy3 afforded the PCy3 complex 4b quantitatively. We examined the ligand exchange reactions of the iridium(III) and rhodium(III) complexes with various phosphines
[IrCl(coe)2 ] 2(coe =环辛烯)与1当量的PN配体(PN = o -Ph 2 PC 6 H 4 CH 2 OCH 2 C 5 H 4 N-2)的反应在室温下膦或吡啶(1当量),得到的中性铱(III)氢化物配合物,(PCN-κ 3 P,C,N)的Ir(H)(Cl)的(大号)(PCN =苯基2 P c ^ 6 ħ 4 C HOCH 2 C 5 H 4 N)[ L = PPh3(1a),PCy 3(1b),PBu 3(1c),PMePh 2(1d),Py(1e)]具有良好的分离产率。PCN配体以子午方式进行配位,这已通过光谱分析和1a的X射线分析得到证实。相关铑(III)氢化物络合物(PCN-κ 3 P,C,N)的Rh(H)(Cl)的(大号)(PCN =苯基2 P c ^ 6 ħ 4 Ç HOCH 2 C ^ 5 ħ 4 Ñ)[大号= PPh 3(4a),PCy 3(4b)]也由[RhCl(coe)2
Direct Observation of Reversible C(sp<sup>3</sup>)−H Bond Activation. Characterization of the Structures of Both Ir Complexes before and after C−H Bond Activation by Using a Flexible P−N Heterochelate Hybrid Ligand
作者:Yasutaka Kataoka、Masahiro Imanishi、Tsuneaki Yamagata、Kazuhide Tani
DOI:10.1021/om990443f
日期:1999.8.1
Direct observation of reversible C-H bond activation of a C(sp(3))-H bond is shown for the Ir(I) complex 2a, which has a coordinatively flexible heterochelate hybrid PNn=1 ligand (la). Full characterization data for the Ir(I) and Ir(III) complexes, including their X-ray structures and estimation of the thermodynamic and kinetic parameters for the C-H bond activation, are provided.
Synthesis, characterisation and structure of square-planar palladium(<scp>II</scp>) complexes with phosphine–pyridine hybrid ligands o-Ph<sub>2</sub>PC<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>O(CH<sub>2</sub>)<sub>n</sub>C<sub>5</sub>H<sub>4</sub>N-2 (n= 1–3). Isolation of the first transition-metal complex with a trans-chelating bidentate PN ligand
but the ligands with longer bridges gave the trans complexes 2 and 3 respectively as the main products. From the reaction of the palladium(II) complex with o-Ph2PC6H4CH2O(CH2)nC5H4N-2 (n= 2 or 3) the trinuclearcomplexes [Pd3Cl6o-Ph2PC6H4CH2O-(CH2)nC5H4N-2}2]4(n= 2) and 5(n= 3) were also obtained as minor products and the cis-chelated complexes analogous to 1 could not be isolated. The reaction of Na2[PdCl4]
钠的反应2 [的PdCl 4 ]或[的PdCl 2(PHCN)2 ]与具有P和能够A N施主原子新的二齿配位体的混合等摩尔量的反式螯合,ö -Ph 2 PC 6 H ^ 4 CH 2 O(CH 2)n C 5 H 4 N-2(n = 1-3),主要产生1:1的配合物[PdCl 2 o -Ph 2 PC 6 H 4 CH 2 O(CH 2)nC 5 H 4 N-2}]。根据连接膦基和吡啶基的主链的长度,主要形成顺式或反式配位的配合物。当n= 1时,形成顺式配合物1,但是具有较长桥的配体分别给出反式配合物2和3作为主要产物。由钯(II)配合物与邻-Ph 2 PC 6 H 4 CH 2 O(CH 2)n C反应生成5 H 4 N-2( n = 2或3)三核配合物[Pd 3 Cl 6 o -Ph 2 PC 6 H 4 CH 2 O-(CH 2) n C 5 H 4 N-2} 2 ] 4( n
Intramolecular C–H and C–O Bond Activation of Dimethylplatinum(II) Complexes Having the PN Ligand
作者:Yasutaka Kataoka、Tatsuya Nakamura、Kazuhide Tani
DOI:10.1246/cl.2003.66
日期:2003.1
Reaction of (cod)PtMe2 with 1 equiv and 2 equiv of the PN ligand (PN = o-Ph2PC6H4CH2OCH2C5H4N-2) (1) gave cis-(PN-κP:κN)PtMe2 (2) and cis-(PN-κP)2PtMe2 (3) respectively. The complex 2 underwent activation of the benzylic C–H bond in toluene at 110 °C to afford (PCN-κP:κC:κN)PtMe (4). Toluene solution of 3 was refluxed for 42 h in the presence of 2 equiv of the PN ligand to afford the C–O bond cleavage product cis-(PN-κP)(Ph2PC6H4CH2-κP:κC)PtMe (cis-5) along with cis-(PN-κP)(PCN-κP:κC)PtMe (cis-6).