水溶性1,2-双（双（羟烷基）膦基）乙烷配体及其镍（II）、钌（III）和铑（I）配合物的合成与表征

Synthesis and Characterization of Water-Soluble 1,2-Bis(bis(hydroxyalkyl)phosphino)ethane Ligands and Their Nickel(II), Ruthenium(III), and Rhodium(I) Complexes.

作者信息

Baxley Gregory T., Miller Warren K., Lyon David K., Miller Brian E., Nieckarz Gregory F., Weakley Timothy J. R., Tyler David R.

机构信息

Department of Chemistry, University of Oregon, Eugene, Oregon 97403-1253, Bend Research, 64550 Research Road, Bend, Oregon 97701-8599, and Department of Chemistry, Wheaton College, Wheaton, Illinois 60187.

出版信息

Inorg Chem. 1996 Nov 6;35(23):6688-6693. doi: 10.1021/ic960766t.

DOI:10.1021/ic960766t

PMID:11666830

Abstract

The syntheses of the water-soluble, chelating phosphines 1,2-bis(bis(hydroxybutyl)phosphino)ethane (1, n = 3; DHBuPE) and 1,2-bis(bis(hydroxypentyl)phosphino)ethane (1, n = 4; DHPePE) are reported. These ligands (and, in general, other 1,2-bis(bis(hydroxyalkyl)phosphino)ethane ligands) can be used to impart water solubility to metal complexes. As examples of this, the [Ni(DHPrPE)(2)Cl]Cl (2), [Rh(DHPrPE)(2)][Cl] (3), and [Ru(DHBuPE)(2)Cl(2)][Cl] (4) complexes were synthesized; they are indeed soluble in water (>0.5 M). Crystals of DHPrPE (1, n = 2) are monoclinic, space group P2(1)/c, with a = 9.5935(8) Å, b = 9.353(2) Å, c = 10.655(2) Å, alpha = 90 degrees, beta = 100.03(1) degrees, gamma = 90, V = 941.5(5) Å(3), R = 0.051, and Z = 2. Crystals of [Ni(DHPrPE)(2)Cl]Cl (2) are monoclinic, space group I2, with a = 15.951(3) Å, b = 11.454(2) Å, c = 20.843(3) Å, alpha = 90 degrees, beta = 91.24(2) degrees, gamma = 90 degrees, V = 3807(2) Å(3), R = 0.062, and Z = 4. Crystals of [Rh(DHPrPE)(2)][Cl] (3) are triclinic, space group P&onemacr;, with a = 13.900(2) Å, b = 15.378(2) Å, c = 18.058(2) Å, alpha = 87.71(1) degrees, beta = 75.03(1) degrees, gamma = 85.24(1), V = 3715(2) Å(3), R = 0.044, and Z = 4. Crystals of [Ru(DHBuPE)(2)Cl(2)][Cl] (4) are monoclinic, space group C2/c, with a = 14.310(2) Å, b = 21.630(2) Å, c = 15.459(3) Å, alpha = 90 degrees, beta = 99.83(1) degrees, gamma = 90, V = 4715(1) Å(3), R = 0.056, and Z = 4.

摘要

报道了水溶性螯合膦1,2 - 双（双（羟丁基）膦基）乙烷（1，n = 3；DHBuPE）和1,2 - 双（双（羟戊基）膦基）乙烷（1，n = 4；DHPePE）的合成。这些配体（以及一般的其他1,2 - 双（双（羟烷基）膦基）乙烷配体）可用于赋予金属配合物水溶性。作为示例，合成了配合物[Ni(DHPrPE)(2)Cl]Cl（2）、[Rh(DHPrPE)(2)][Cl]（3）和[Ru(DHBuPE)(2)Cl(2)][Cl]（4）；它们确实可溶于水（>0.5 M）。DHPrPE（1，n = 2）的晶体为单斜晶系，空间群P2(1)/c，a = 9.5935(8) Å，b = 9.353(2) Å，c = 10.655(2) Å，α = 90°，β = 100.03(1)°，γ = 90°，V = 941.5(5) Å(3)，R = 0.051，Z = 2。[Ni(DHPrPE)(2)Cl]Cl（2）的晶体为单斜晶系，空间群I2，a = 15.951(3) Å，b = 11.454(2) Å，c = 20.843(3) Å，α = 90°，β = 91.24(2)°，γ = 90°，V = 3807(2) Å(3)，R = 0.062，Z = 4。[Rh(DHPrPE)(2)][Cl]（3）的晶体为三斜晶系，空间群P&onemacr;，a = 13.900(2) Å，b = 15.378(2) Å，c = 18.058(2) Å, α = 87.71(1)°，β = 75.03(1)°，γ = 85.24(1)，V = 3715(2) Å(3)，R = 0.044，Z = 4。[Ru(DHBuPE)(2)Cl(2)][Cl]（4）的晶体为单斜晶系，空间群C2/c，a = 14.310(2) Å，b = 21.630(2) Å，c = 15.459(3) Å，α = 90°，β = 99.83(1)°，γ = 90°，V = 4715(1) Å(3)，R = 0.056，Z = 4。