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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >ortho-Metallated complexes of platinum(II) and diplatinum(I) containing the carbanions (2-diphenylphosphino) phenyl and (2-diphenylphosphino)-n-tolyl (n=5, 6)
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ortho-Metallated complexes of platinum(II) and diplatinum(I) containing the carbanions (2-diphenylphosphino) phenyl and (2-diphenylphosphino)-n-tolyl (n=5, 6)

机译：含有碳负离子（2-二苯基膦基）苯基和（2-二苯基膦基）-n-甲苯基的铂（II）和二铂（I）的邻位金属化配合物（n = 5，6）

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When the ortho-metallated complexes cis-[Pt(kappa(2)-C6H3-5-R-2-PPh2)(2)] ( R= H 1, Me 2) are either heated in toluene or treated with CO at room temperature, one of the four- membered chelate rings is opened irreversibly to give dinuclear isomers [Pt-2(kappa(2)-C6H3-5-R-2-PPh2)(2)(mu-C6H3-5-R-2-PPh2)(2)] ( R= H 10, Me 11). A single- crystal X-ray diffraction study shows the Pt center dot center dot center dot Pt separation in 10 to be 3.3875(4) angstrom. By-products of the reactions of 1 and 2 with CO are polymeric isomers (R = H 13, Me 14) in which one of the P-C ligands is believed to bridge adjacent platinum atoms intermolecularly. In contrast to the behaviour of 1 and 2, when cis-[Pt(kappa(2)-C6H3-6-Me-2-PPh2)(2)] (cis-3) is heated in toluene, the main product is trans-3, and reaction of cis-3 with CO gives a carbonyl complex [Pt(CO)(kappa(1)-C-C6H3-6-Me-2-PPh2)(kappa(2)-C6H3-6-Me-2-PPh2)] 15, in which one of the carbanions is coordinated only through the carbon. Formation of a dimer analogous to 10 or 11 is sterically hindered by the 6-methyl substituent. Comproportionation of 1 or 2 with [Pt(PPh3)(2)L] (L = PPh3, C2H4) gives diplatinum(I) complexes [Pt-2(mu-C6H3-5-R-2-PPh2)(2)(PPh3)(2)] (R= H 16, Me 17). An X-ray diffraction study shows that 17 contains a pair of planar-coordinated metal atoms separated by 2.61762(16) angstrom. There is no evidence for the formation of an analogue containing mu-C6H3-6-Me-2-PPh2. The axial PPh3 ligands of 16 are readily replaced by (BuNC)-N-t giving [Pt-2(mu-2-C6H4PPh2)(2)(CNBut)(2)] 18, which is protonated by HBF4 to form a mu- hydridodiplatinum(II) salt [Pt-2(mu-H)(mu-2-C6H4PPh2)(2)(CNBut)(2)]BF4 [21] BF4. The J(PtPt) values in [21]BF4 and 18, 2700 Hz and 4421 Hz, respectively, reflect the weakening of the Pt-Pt interaction caused by protonation. Similarly, 16 and 17 react with the electrophiles iodine and strong acids to give salts of general formula [Pt-2(mu-Z)(mu-C6H3-5-R-2-PPh2)(2)(PPh3)(2)] Y (Y = Z = I, R = H 19(+), Me 20(+); Z = H, Y = BF4, PF6, OTf, R = H 22(+); Z = H, Y = PF6, R = Me 23(+)). A single-crystal X-ray diffraction study of [23]PF6 shows that the cation has an approximately A-frame geometry, with a Pt center dot center dot center dot Pt separation of 2.7888(3) angstrom and a Pt-H bond length of 1.62(1) angstrom, and that the 5-methyl substituents have undergone partial exchange with the 4-hydrogen atoms of the PPh2 groups of the bridging carbanion. The latter observation indicates that the added proton of [23](+) undergoes a reversible reductive elimination-oxidative addition sequence with the Pt-C(aryl) bonds.
机译：当将邻位金属配合物顺式[[Pt（kappa（2）-C6H3-5-R-2-PPh2）（2）]（R = H 1，Me 2）在甲苯中加热或在室温下用CO处理温度下，四元螯合环之一不可逆地打开，得到双核异构体[Pt-2（kappa（2）-C6H3-5-R-2-PPh2）（2）（mu-C6H3-5-R-2 -PPh2）（2）]（R ＝ H 10，Me 11）。单晶X射线衍射研究显示，Pt中心点中心点中心点Pt的间距在10处为3.3875（4）埃。 1和2与CO反应的副产物是聚合异构体（R = H 13，Me 14），其中一种P-C配体被认为能桥连相邻的铂原子。与1和2的行为相反，当在甲苯中加热cis- [Pt（kappa（2）-C6H3-6-Me-2-PPh2）（2）]（cis-3）时，主要产物是反式-3，顺式3与CO反应生成羰基络合物[Pt（CO）（kappa（1）-C-C6H3-6-Me-2-PPh2）（kappa（2）-C6H3-6-Me- 2-PPh2）] 15，其中一个碳负离子仅通过碳进行配位。 6-甲基取代基在空间上阻碍了类似于10或11的二聚物的形成。将1或2与[Pt（PPh3）（2）L]（L = PPh3，C2H4）相称得到二铂（I）络合物[Pt-2（mu-C6H3-5-R-2-PPh2）（2）（ PPh3）（2）]（R = H 16，Me 17）。 X射线衍射研究表明17包含一对以2.61762（16）埃隔开的平面配位金属原子。没有证据表明含有mu-C6H3-6-Me-2-PPh2的类似物的形成。 16的轴向PPh3配体很容易被（BuNC）-Nt取代，得到[Pt-2（mu-2-C6H4PPh2）（2）（CNBut）（2）] 18，该基团被HBF4质子化，形成muhydridodiplatinum （II）盐[Pt-2（mu-H）（mu-2-C6H4PPh2）（2）（CNBut）（2）] BF4 [21] BF4。 [21] BF4和18、2700 Hz和4421 Hz中的J（PtPt）值分别反映了质子化引起的Pt-Pt相互作用的减弱。同样，16和17与亲电子碘和强酸反应，生成通式[Pt-2（mu-Z）（mu-C6H3-5-R-2-PPh2）（2）（PPh3）（2）的盐] Y（Y = Z = I，R = H 19（+），Me 20（+）; Z = H，Y = BF4，PF6，OTf，R = H 22（+）; Z = H，Y = PF6 ，R ＝ Me 23（+））。 [23] PF6的单晶X射线衍射研究表明，该阳离子具有近似A构架的几何结构，Pt中心点中心点中心点Pt间距为2.7888（3）埃，Pt-H键长的碳原子数为1.62（1）埃，并且5-甲基取代基已与桥连碳负离子的PPh2基团的4-氢原子部分交换。后一观察表明，[23]（+）的添加质子经历了具有Pt-C（芳基）键的可逆还原消除-氧化添加序列。

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