Yamamoto Yasuhiro, Sato Ryoichi, Matsuo Fumiko, Sudoh Chihiro, Igoshi Toshiaki
Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, 274 Japan.
Inorg Chem. 1996 Apr 10;35(8):2329-2336. doi: 10.1021/ic950625b.
Reactions of (eta(6)-arene)RuCl(2) 1 (arene = p-cymene (a), 1,2,3,4-Me(4)C(6)H(2) (b), 1,2,3-Me(3)C(6)H(2) (c)) with tris(2,6-dimethoxyphenyl)phosphine (TDMPP) led to loss of two molecules of CH(3)Cl to give (eta(6)-arene)Ru[{2-O-C(6)H(3)-6-OMe}(2){C(6)H(3)(OMe)(2)-2,6}], 2a-c, which contains a trihapto ligand (eta(3)-P,O,O) derived from TDMPP, whereas the 1,3,5-Me(3)C(6)H(3) (1d), 1,2,3,5-Me(4)C(6)H(2) (1e), and C(6)Me(6) (1f) complexes did not react with TDMPP. The structures of 2a and 2b were confirmed by X-ray analyses: for 2a, a = 11.691(2) Å, b = 15.228(2) Å, c = 10.320(1) Å, alpha = 95.93(1) degrees, beta = 113.783(9) degrees, gamma = 83.86(1) degrees, triclinic, P&onemacr;, Z = 2, R = 0.051; for 2b, a = 17.79(2) Å, b = 15.43(1) Å, c = 20.93(1) Å, beta = 91.25(8) degrees, monoclinic, P2(1)/n, Z = 8, R = 0.056. Bis(2,6-dimethoxyphenyl)phenylphosphine (BDMPP) reacted with 1a, 1b, and 1d at room temperature to give (eta(6)-arene)RuCl[PPh(2-O-C(6)H(3)-6-OMe){C(6)H(3)(OMe)(2)-2,6}], 3a,b,d, which contains a dihapto (eta(2)-P,O) ligand derived from BDMPP by an X-ray analysis of 3a: a = 12.33(1) Å, b = 14.246(8) Å, c = 11.236(9) Å, alpha = 91.47(8) degrees, beta = 117.28(6) degrees, gamma = 111.70(6) degrees, triclinic, P&onemacr;, Z = 2, R = 0.040. A similar reaction with 1f recovered the starting materials, but that in refluxing MeCN produced [(eta(6)-C(6)Me(6))Ru[PPh(2-O-C(6)H(3)-6-OMe}(2)], 4f, containing a trihapto (eta(3)-P,O,O) ligand derived from BDMPP. Complex 1d reacted with BDMPP at reflux in MeCN/CH(2)Cl(2) and resulted in a loss of an arene ring to give a five-coordinate complex, Rueta(2)-P,O-PPh(2-O-C(6)H(3)-6-OMe){C(6)H(3)(OMe)(2)-2,6}(MeCN), 5. Treatment of (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP) with 1f gave (eta(6)-C(6)Me(6))RuCl[eta(2)-P,O-PPh(2)(2-O-C(6)H(3)-6-OMe)],6f, and that with 1b gave (eta(6)-1,2,3,4-Me(4)C(6)H(2))RuCl[eta(2)-P,O-PPh(2)(2-O-C(6)H(3)-6-OMe}], 6b, and (eta(6)-1,2,3,4-Me(4)C(6)H(2))RuCl(2)[eta(1)-P-PPh(2){C(6)H(3)(OMe)(2)-2,6}],7b. The phosphine ligand of 6b acted as a bidentate ligand derived from MDMPP: a = 8.074(4) Å, b = 16.816(3) Å, c = 18.916(4) Å, beta = 94.05(3) degrees, monoclinic, P2(1)/n, Z = 4, R = 0.051. Transformation of 7b to 6b readily occurred accompanying an elimination of MeCl. Reaction of 1a with MDMPP eliminated an arene ring to give the octahedral compound RuCl(2)eta(2)-P,OMe-PPh(2){C(6)H(3)(MeO)(2)-2,6}, 8. An X-ray analysis of 8 showed that two MDMPP ligands were in a cis-position: a = 10.596(14) Å, b = 27.586(12) Å, c = 13.036(8) Å, beta = 108.17(7) degrees, monoclinic, P2(1)/n, Z = 4, R = 0.035.
[（η⁶-芳烃）RuCl₂]₂ 1（芳烃 = 对异丙基苯（a）、1,2,3,4-Me₄C₆H₂（b）、1,2,3-Me₃C₆H₂（c））与三（2,6-二甲氧基苯基）膦（TDMPP）反应，导致两分子CH₃Cl失去，生成（η⁶-芳烃）Ru[{2-O-C₆H₃-6-OMe}₂{C₆H₃(OMe)₂-2,6}]，2a - c，其包含一个源自TDMPP的三齿配体（η³-P,O,O），而1,3,5-Me₃C₆H₃（1d）、1,2,3,5-Me₄C₆H₂（1e）和C₆Me₆（1f）配合物不与TDMPP反应。通过X射线分析确定了2a和2b的结构：对于2a，a = 11.691(2) Å，b = 15.228(2) Å，c = 10.320(1) Å，α = 95.93(1)°，β = 113.783(9)°，γ = 83.86(1)°，三斜晶系，P&onemacr;，Z = 2，R = 0.051；对于2b，a = 17.79(2) Å，b = 15.43(1) Å，c = 20.93(1) Å，β = 91.25(8)°，单斜晶系，P2(1)/n，Z = 8，R = 0.056。双（2,6-二甲氧基苯基）苯基膦（BDMPP）在室温下与1a、1b和1d反应，生成（η⁶-芳烃）RuCl[PPh(2-O-C₆H₃-6-OMe){C₆H₃(OMe)₂-2,6}]，3a,b,d，通过对3a的X射线分析可知其包含一个源自BDMPP的双齿（η²-P,O）配体：a = 12.33(1) Å，b = 14.246(8) Å，c = 11.236(9) Å，α = 91.47(8)°，β = 117.28(6)°，γ = 111.70(6)°，三斜晶系，P&onemacr;，Z = 2，R = 0.040。与1f的类似反应回收了起始原料，但在回流的MeCN中反应生成了[(η⁶-C₆Me₆)Ru[PPh(2-O-C₆H₃-6-OMe}(2)]，4f，其包含一个源自BDMPP的三齿（η³-P,O,O）配体。配合物1d在MeCN/CH₂Cl₂中回流时与BDMPP反应，导致一个芳烃环失去，生成五配位配合物Ruη²-P,O-PPh(2-O-C₆H₃-6-OMe){C₆H₃(OMe)₂-2,6}(MeCN)，5。用（2,6-二甲氧基苯基）二苯基膦（MDMPP）处理1f得到（η⁶-C₆Me₆）RuCl[η²-P,O-PPh(2)(2-O-C₆H₃-6-OMe)]，6f，用其处理1b得到（η⁶-1,2,3,4-Me₄C₆H₂）RuCl[η²-P,O-PPh(2)(2-O-C₆H₃-6-OMe)]，6b，以及（η⁶-1,2,3,4-Me₄C₆H₂）RuCl₂[η¹-P-PPh(2){C₆H₃(OMe)₂-2,6}]，7b。6b的膦配体作为源自MDMPP的双齿配体：a = 8.074(4) Å，b = 16.816(3) Å，c = 18.916(4) Å，β = 94.05(3)°，单斜晶系，P2(1)/n，Z = 4，R = 0.051。7b伴随MeCl的消除很容易转化为6b。
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