Cavell Ronald G., Hilts Robert W., Luo Hongyan, McDonald Robert
Contribution from the Department of Chemistry, University of Alberta, Edmonton, AB, Canada T6G 2G2.
Inorg Chem. 1999 Mar 8;38(5):897-905. doi: 10.1021/ic980304a.
The silylated aryloxo ligands bis(o-silyloxyphenyl)phenylphosphine (abbreviated PhP{OT}(2)) and tris(o-trimethylsilyloxyphenyl)phosphine (abbreviated P{OT}(3), where T = Me(3)Si) were prepared. Complexation reactions with O=ReCl(2)(OEt)(PPh(3))(2) and O=ReCl(3)(PPh(3))(2) proceed by displacement of one PPh(3) and the subsequent stepwise replacement of the OEt and/or Cl substituents. The new complex Re(O)Cl(2)kappa(2)-(P,O)-(PhP{O}{OT}), formed by elimination of Me(3)SiOEt, exists in diastereomeric cis and trans forms. Elimination of a second equivalent of Me(3)SiCl gives Re(O)Clkappa(3)-(P,O,O)-(PhP{O}(2)). Similarly P{OT}(3) converts Re(O)Cl(2)(OEt)(PPh(3))(2) to ReOCl(2)kappa(2)-(P,O)-(P{O}{OT}(2)) (5) (structurally characterized as 5.0.875CH(2)Cl(2)): crystal data; triclinic P&onemacr;, a = 14.302(4) Å, b = 18.734(2) Å, c = 17.639(4) Å, alpha = 80.950(12) degrees, beta = 80.12(2) degrees, gamma = 81.76(2) degrees, Z = 4. Final R(1) and wR(2) values are 0.0852 and 0.1525, respectively on F(o)(2) > 2sigma(F(o)(2)) data (or 0.1948 and 0.2019 on all data). The phenoxy phosphine ligand in 5 is bound via P and one O to Re. The P atoms are mutually cis to each other and to the terminal oxygen on Re. Two ortho-trimethylsiloxy substituted phenyl rings dangle from the coordinated phosphorus atom. Complex 5 can be converted to Re(O)Clkappa(3)-(P,O,O)-(P{O}(2){OT}) (6) by treatment with PPN(+) Cl(-) and 6 was also obtained by direct reaction of Re(O)Cl(3)(PPh(3))(2) with P{OT}(3) at higher temperatures. The complex 6 has been structurally characterized: crystal data triclinic, P&onemacr;, a = 10.1509(6) Å, b = 12.1123(8) Å, c = 16.2142(14) Å, alpha = 97.851(7) degrees, beta = 94.852(7) degrees, gamma = 96.889(6) degrees, Z = 2. Final R(1) and wR(2) values were 0.0303 and 0.0721 on F(o)(2) > 2sigma(F(o)(2)) data (or 0.0348 and 0.0742 on all data). The phenoxyphosphine ligand in 6 is bound facially to Re through P and two of the phenoxy oxygens. The Ph(3)P group and terminal oxygen atoms are cis to the oxygen atoms of the phenoxy ligands and the Cl lies trans to P. One trimethylsiloxyphenol group dangles. Careful hydrolysis of 6 gave Re(O)Clkappa(3)-(P,O,O)-(P{O}(2){OH}) which was also formed during complexation reactions in moist solvent. Solution (31)P{(1)H} NMR demonstrated cis- or trans-(P,P) geometry for the complexes, which was confirmed in the two aforementioned cases by structure determinations.
制备了硅烷基化芳氧基配体双（邻硅烷氧基苯基）苯基膦（缩写为PhP{OT}(2)）和三（邻三甲基硅烷氧基苯基）膦（缩写为P{OT}(3)，其中T = Me(3)Si）。与O=ReCl(2)(OEt)(PPh(3))(2)和O=ReCl(3)(PPh(3))(2)的络合反应通过一个PPh(3)的取代以及随后EtO和/或Cl取代基的逐步取代进行。通过消除Me(3)SiOEt形成的新络合物Re(O)Cl(2)κ(2)-(P,O)-(PhP{O}{OT})以非对映体的顺式和反式形式存在。消除第二当量的Me(3)SiCl得到Re(O)Clκ(3)-(P,O,O)-(PhP{O}(2))。类似地，P{OT}(3)将Re(O)Cl(2)(OEt)(PPh(3))(2)转化为ReOCl(2)κ(2)-(P,O)-(P{O}{OT}(2)) (5)（结构表征为5·0.875CH(2)Cl(2)）：晶体数据；三斜晶系P&onemacr;，a = 14.302(4) Å，b = 18.734(2) Å，c = 17.639(4) Å，α = 80.950(12)°，β = 80.12(2)°，γ = 81.76(2)°，Z = 4。在F(o)(2) > 2σ(F(o)(2))数据上最终的R(1)和wR(2)值分别为0.0852和0.1525（或在所有数据上为0.1948和0.2019）。5中的苯氧基膦配体通过P和一个O与Re结合。P原子彼此相互顺式且与Re上的末端氧顺式。两个邻位三甲基硅氧基取代的苯环从配位的磷原子上悬垂。通过用PPN(+)Cl(-)处理，络合物5可以转化为Re(O)Clκ(3)-(P,O,O)-(P{O}(2){OT}) (6)，并且6也通过在较高温度下Re(O)Cl(3)(PPh(3))(2)与P{OT}(3)直接反应得到。络合物6已进行结构表征：晶体数据三斜晶系，P&onemacr;，a = 10.1509(6) Å，b = 12.1123(8) Å，c = 16.2142(14) Å，α = 97.851(7)°，β = 94.852(7)°，γ = 96.889(6)°，Z = 2。在F(o)(2) > 2σ(F(o)(2))数据上最终的R(1)和wR(2)值分别为0.0303和0.0721（或在所有数据上为0.0348和0.0742）。6中的苯氧基膦配体通过P和两个苯氧基氧原子以面式与Re结合。Ph(3)P基团和末端氧原子与苯氧基配体的氧原子顺式，且Cl与P反式。一个三甲基硅氧基酚基团悬垂。对6进行小心水解得到Re(O)Clκ(3)-(P,O,O)-(P{O}(2){OH})，其也在潮湿溶剂中的络合反应过程中形成。溶液(31)P{(1)H} NMR表明络合物具有顺式或反式-(P,P)几何构型，并在上述两种情况下通过结构测定得到证实。
