Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal-Mercury (d8-d10) Cyclometalated Complexes Containing 2-C6H4PPh2<
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- 作者：Martin A. Bennett ; Maria Contel ; David C. R. Hockless ; Lee L. Welling ; and Anthony C. Willis
- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：February 25, 2002
- 年：2002
- 卷：41
- 期：4
- 页码：844 - 855
- 全文大小：200K
- 年卷期：v.41,no.4(February 25, 2002)
- ISSN：1520-510X
文摘
Treatment of HgCl2 with 2-LiC6H4PPh2 gives [Hg(2-C6H4PPh2)2] (1), whose phosphorus atoms take up oxygen,sulfur, and borane to give the compounds [Hg{2-C6H4P(X)Ph2}2] [ X = O (3), S (4), and BH3 (5)], respectively.Compound 1 functions as a bidentate ligand of wide, variable bite angle that can span either cis or trans coordinationsites in a planar complex. Representative complexes include [HgX2·1] [X = Cl (6a), Br (6b)], cis-[PtX2·1] [X = Cl(cis-7), Me (9), Ph (10)], and trans-[MX2·1] [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 dispositionof 1 in complexes trans-7, 8, and 11 imposes close metal-mercury contacts [2.8339(7), 2.8797(8), and 2.756(8)Å, respectively] that are suggestive of a donor-acceptor interaction, M 
rarr.gif"> Hg. Prolonged heating of 1 with [PtCl2(cod)]gives the binuclear cyclometalated complex [(
rs/eta.gif" BORDER=0 >2-2-C6H4PPh2)Pt(
r.gif">-2-C6H4PPh2)2HgCl] (14) from which the salt [(rs/eta.gif" BORDER=0 >2-2-C6H4PPh2)Pt(r.gif">-2-C6H4PPh2)2Hg]PF6 (15) is derived by treatment with AgPF6. In 14 and 15, the r.gif">-C6H4PPh2groups adopt a head-to-tail arrangement, and the Pt-Hg separation in 14, 3.1335(5) Å, is in the range expectedfor a weak metallophilic interaction. A similar arrangement of bridging groups is found in [Cl(nBu3P)Pd(r.gif">-2-C6H4PPh2)2HgCl] (16), which is formed by heating 1 with [PdCl2(PnBu3)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-C6H4PPh2){2-C6H4P(O)Ph2}]. On heating, 19 eliminates Pd and Hg, and the C-C coupled product 2-Ph2PC6H4C6H4PPh2-2 (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(rs/eta.gif" BORDER=0 >1-C-2-C6H4PPh2)(rs/eta.gif" BORDER=0 >2-2-C6H4PPh2)(rs/eta.gif" BORDER=0 >1-P-1)]. Crystal data are as follows. Compound 3:monoclinic, P21/n, with a = 11.331(3) Å, b = 9.381(2) Å, c = 14.516 Å, rs/beta2.gif" BORDER=0 ALIGN="middle"> = 98.30(2)
, and Z = 2. Compound6b·2CH2Cl2: triclinic, P
r.gif">, with a = 12.720(3) Å, b = 13.154(3) Å, c = 12.724(2) Å, rs/alpha.gif" BORDER=0> = 92.01(2), rs/beta2.gif" BORDER=0 ALIGN="middle"> = 109.19(2),rs/gamma.gif" BORDER=0 > = 90.82(2), and Z = 2. Compound trans-7·2CH2Cl2: orthorhombic, Pbca, with a = 19.805(3) Å, b = 8.532(4)Å, c = 23.076(2) Å, and Z = 4. Compound 11·2CH2Cl2: orthorhombic, Pbca, with a = 19.455(3) Å, b = 8.496(5)Å, c = 22.858(3) Å, and Z = 4. Compound 14: monoclinic, P21/c, with a = 13.150(3) Å, b = 12.912(6) Å, c =26.724(2) Å, rs/beta2.gif" BORDER=0 ALIGN="middle"> = 94.09(1), and Z = 4. Compound 20·C6H5CH3.0.5CH2Cl2: triclinic, Pr.gif">, with a = 13.199(1) Å,b = 15.273(2) Å, c = 17.850(1) Å, rs/alpha.gif" BORDER=0> = 93.830(7), rs/beta2.gif" BORDER=0 ALIGN="middle"> = 93.664(6), rs/gamma.gif" BORDER=0 > = 104.378(7), and Z = 2.
rarr.gif"> Hg. Prolonged heating of 1 with [PtCl2(cod)]gives the binuclear cyclometalated complex [(rs/eta.gif" BORDER=0 >2-2-C6H4PPh2)Pt(r.gif">-2-C6H4PPh2)2HgCl] (14) from which the salt [(rs/eta.gif" BORDER=0 >2-2-C6H4PPh2)Pt(r.gif">-2-C6H4PPh2)2Hg]PF6 (15) is derived by treatment with AgPF6. In 14 and 15, the r.gif">-C6H4PPh2groups adopt a head-to-tail arrangement, and the Pt-Hg separation in 14, 3.1335(5) Å, is in the range expectedfor a weak metallophilic interaction. A similar arrangement of bridging groups is found in [Cl(nBu3P)Pd(r.gif">-2-C6H4PPh2)2HgCl] (16), which is formed by heating 1 with [PdCl2(PnBu3)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-C6H4PPh2){2-C6H4P(O)Ph2}]. On heating, 19 eliminates Pd and Hg, and the C-C coupled product 2-Ph2PC6H4C6H4PPh2-2 (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(rs/eta.gif" BORDER=0 >1-C-2-C6H4PPh2)(rs/eta.gif" BORDER=0 >2-2-C6H4PPh2)(rs/eta.gif" BORDER=0 >1-P-1)]. Crystal data are as follows. Compound 3:monoclinic, P21/n, with a = 11.331(3) Å, b = 9.381(2) Å, c = 14.516 Å, rs/beta2.gif" BORDER=0 ALIGN="middle"> = 98.30(2), and Z = 2. Compound6b·2CH2Cl2: triclinic, Pr.gif">, with a = 12.720(3) Å, b = 13.154(3) Å, c = 12.724(2) Å, rs/alpha.gif" BORDER=0> = 92.01(2), rs/beta2.gif" BORDER=0 ALIGN="middle"> = 109.19(2),rs/gamma.gif" BORDER=0 > = 90.82(2), and Z = 2. Compound trans-7·2CH2Cl2: orthorhombic, Pbca, with a = 19.805(3) Å, b = 8.532(4)Å, c = 23.076(2) Å, and Z = 4. Compound 11·2CH2Cl2: orthorhombic, Pbca, with a = 19.455(3) Å, b = 8.496(5)Å, c = 22.858(3) Å, and Z = 4. Compound 14: monoclinic, P21/c, with a = 13.150(3) Å, b = 12.912(6) Å, c =26.724(2) Å, rs/beta2.gif" BORDER=0 ALIGN="middle"> = 94.09(1), and Z = 4. Compound 20·C6H5CH3.0.5CH2Cl2: triclinic, Pr.gif">, with a = 13.199(1) Å,b = 15.273(2) Å, c = 17.850(1) Å, rs/alpha.gif" BORDER=0> = 93.830(7), rs/beta2.gif" BORDER=0 ALIGN="middle"> = 93.664(6), rs/gamma.gif" BORDER=0 > = 104.378(7), and Z = 2.