双[(2-二苯基膦基)苯基]汞：一种磷供体配体以及含2-C₆H₄PPh₂的混合金属-汞（d⁸-d¹⁰）环金属化配合物的前体。
Bis[(2-diphenylphosphino)phenyl]mercury: a P-donor ligand and precursor to mixed metal-mercury (d(8)-d(10)) cyclometalated complexes containing 2-C(6)H(4)PPh(2).
作者信息
Bennett Martin A, Contel Maria, Hockless David C R, Welling Lee L, Willis Anthony C
机构信息
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
出版信息
Inorg Chem. 2002 Feb 25;41(4):844-55. doi: 10.1021/ic010890z.
Treatment of HgCl(2) with 2-LiC(6)H(4)PPh(2) gives [Hg(2-C(6)H(4)PPh(2))(2)] (1), whose phosphorus atoms take up oxygen, sulfur, and borane to give the compounds [Hg2-C(6)H(4)P(X)Ph(2)] [ X = O (3), S (4), and BH(3) (5)], respectively. Compound 1 functions as a bidentate ligand of wide, variable bite angle that can span either cis or trans coordination sites in a planar complex. Representative complexes include [HgX(2) x 1] [X = Cl (6a), Br (6b)], cis-[PtX(2) x 1] [X = Cl (cis-7), Me (9), Ph (10)], and trans-[MX(2) x 1] [X = Cl, M = Pt (trans-7), Pd (8), Ni (11); X = NCS, M = Ni (13)] in which the central metal ions are in either tetrahedral (6a,b) or planar (7-11, 13) coordination. The trans disposition of 1 in complexes trans-7, 8, and 11 imposes close metal-mercury contacts [2.8339(7), 2.8797(8), and 2.756(8) A, respectively] that are suggestive of a donor-acceptor interaction, M --> Hg. Prolonged heating of 1 with [PtCl(2)(cod)] gives the binuclear cyclometalated complex [(eta(2)-2-C(6)H(4)PPh(2))Pt(mu-2-C(6)H(4)PPh(2))(2)HgCl] (14) from which the salt [(eta(2)-2-C(6)H(4)PPh(2))Pt(mu-2-C(6)H(4)PPh(2))(2)Hg]PF(6) (15) is derived by treatment with AgPF(6). In 14 and 15, the mu-C(6)H(4)PPh(2) groups adopt a head-to-tail arrangement, and the Pt-Hg separation in 14, 3.1335(5) A, is in the range expected for a weak metallophilic interaction. A similar arrangement of bridging groups is found in [Cl((n)Bu(3)P)Pd(mu-C(6)H(4)PPh(2))(2)HgCl] (16), which is formed by heating 1 with [PdCl(2)(P(n)()Bu(3))(2)]. Reaction of 1 with [Pd(dba)(2)] [dba = dibenzylideneacetone] at room temperature gives [Pd(1)(2)] (19) which, in air, forms a trigonal planar palladium(0) complex 20 containing bidentate 1 and the monodentate phosphine-phosphine oxide ligand [Hg(2-C(6)H(4)PPh(2))[2-C(6)H(4)P(O)Ph(2)]]. On heating, 19 eliminates Pd and Hg, and the C-C coupled product 2-Ph(2)PC(6)H(4)C(6)H(4)PPh(2)-2 (18) is formed by reductive elimination. In contrast, 1 reacts with platinum(0) complexes to give a bis(aryl)platinum(II) species formulated as [Pt(eta(1)-C-2-C(6)H(4)PPh(2))(eta(2)-2-C(6)H(4)PPh(2))(eta(1)-P-1)]. Crystal data are as follows. Compound 3: monoclinic, P2(1)/n, with a = 11.331(3) A, b = 9.381(2) A, c = 14.516 A, beta = 98.30(2) degrees, and Z = 2. Compound 6b x 2CH(2)Cl(2): triclinic, P macro 1, with a = 12.720(3) A, b = 13.154(3) A, c = 12.724(2) A, alpha = 92.01(2) degrees, beta = 109.19(2) degrees, gamma = 90.82(2) degrees, and Z = 2. Compound trans-7 x 2CH(2)Cl(2): orthorhombic, Pbca, with a = 19.805(3) A, b = 8.532(4) A, c = 23.076(2) A, and Z = 4. Compound 11 x 2CH(2)Cl(2): orthorhombic, Pbca, with a = 19.455(3) A, b = 8.496(5) A, c = 22.858(3) A, and Z = 4. Compound 14: monoclinic, P2(1)/c, with a = 13.150(3) A, b = 12.912(6) A, c = 26.724(2) A, beta = 94.09(1) degrees, and Z = 4. Compound 20 x C(6)H(5)CH(3).0.5CH(2)Cl(2): triclinic, P macro 1, with a = 13.199(1) A, b = 15.273(2) A, c = 17.850(1) A, alpha = 93.830(7), beta = 93.664(6), gamma = 104.378(7) degrees, and Z = 2.
用2 - LiC₆H₄PPh₂处理HgCl₂得到[Hg(2 - C₆H₄PPh₂)₂]（1），其磷原子可与氧、硫和硼烷反应，分别生成化合物[Hg[2 - C₆H₄P(X)Ph₂]₂] [X = O（3）、S（4）和BH₃（5）]。化合物1作为一种双齿配体，具有宽的、可变的咬角，可跨越平面配合物中的顺式或反式配位位点。代表性的配合物包括[HgX₂·1] [X = Cl（6a）、Br（6b）]、顺式 - [PtX₂·1] [X = Cl（顺式 - 7）、Me（9）、Ph（10）]以及反式 - [MX₂·1] [X = Cl，M = Pt（反式 - 7）、Pd（8）、Ni（11）；X = NCS，M = Ni（13）]，其中中心金属离子处于四面体（6a，b）或平面（7 - 11，13）配位。配合物反式 - 7、8和11中1的反式排列导致了紧密的金属 - 汞接触[分别为2.8339(7)、2.8797(8)和2.756(8) Å]，这表明存在供体 - 受体相互作用，即M→Hg。将1与[PtCl₂(cod)]长时间加热得到双核环金属化配合物[(η² - 2 - C₆H₄PPh₂)Pt(μ - 2 - C₆H₄PPh₂)₂HgCl]（14），用AgPF₆处理该配合物可得到盐[(η² - 2 - C₆H₄PPh₂)Pt(μ - 2 - C₆H₄PPh₂)₂Hg]PF₆（15）。在14和15中，μ - C₆H₄PPh₂基团呈头对尾排列，14中Pt - Hg间距为3.1335(5) Å，处于弱亲金属相互作用预期的范围内。在[Cl((n)Bu₃P)Pd(μ - C₆H₄PPh₂)₂HgCl]（16）中发现了类似的桥连基团排列，它是通过将1与[PdCl₂(P(n)()Bu₃)₂]加热形成的。在室温下，1与[Pd(dba)₂] [dba = 二亚苄基丙酮]反应得到[Pd(1)₂]（19），在空气中，它形成一个含有双齿1和单齿膦 - 膦氧化物配体[Hg(2 - C₆H₄PPh₂)[2 - C₆H₄P(O)Ph₂]]的三角平面钯(0)配合物20。加热时，19消除Pd和Hg，通过还原消除形成C - C偶联产物2 - Ph₂PC₆H₄C₆H₄PPh₂ - 2（18）。相反，1与铂(0)配合物反应得到一种双(芳基)铂(II)物种，其化学式为[Pt(η¹ - C - 2 - C₆H₄PPh₂)(η² - 2 - C₆H₄PPh₂)(η¹ - P - 1)]。晶体数据如下。化合物3：单斜晶系，P2(1)/n，a = 11.331(3) Å，b = 9.381(2) Å，c = 14.516 Å，β = 98.30(2)°且Z = 2。化合物6b·2CH₂Cl₂：三斜晶系，P1̅，a = 12.720(3) Å，b = 13.154(3) Å，c = 12.724(2) Å，α = 92.01(2)°，β = 109.19(2)°，γ = 90.82(2)°且Z = 2。化合物反式 - 7·2CH₂Cl₂：正交晶系，Pbca，a = 19.805(3) Å，b = 8.532(4) Å，c = 23.076(2) Å且Z = 4。化合物11·2CH₂Cl₂：正交晶系，Pbca，a = 19.455(3) Å，b = 8.496(5) Å，c = 22.858(3) Å且Z = 4。化合物14：单斜晶系，P2(1)/c，a = 13.150(3) Å，b = 12.912(6) Å，c = 26.724(2) Å，β = 94.09(1)°且Z = 4。化合物20·C₆H₅CH₃·0.5CH₂Cl₂：三斜晶系，P1̅，a = 13.199(1) Å，b = 15.273(2) Å，c = 17.850(1) Å，α = 93.830(7)，β = 93.664(6)，γ = 104.378(7)°且Z = 2。
Zotero 插件