Mn2(μ-H)(μ-P(cyclo-C6H11)2)(CO)7(ax-H2P(cyclo-C6H11)) | 316803-49-3

• 英文名称: Mn2(μ-H)(μ-P(cyclo-C6H11)2)(CO)7(ax-H2P(cyclo-C6H11))
• CAS: 316803-49-3
• 化学式: C₂₅H₃₆Mn₂O₇P₂
• 分子量: 620.38
• InChiKey: ZSIVFLWDJQKTLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  氯(三乙基膦)金(I) 、 Mn2(μ-H)(μ-P(cyclo-C6H11)2)(CO)7(ax-H2P(cyclo-C6H11)) 在 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) 作用下， 以 四氢呋喃 为溶剂， 以26%的产率得到Mn2(AuP(C2H5)3)2(μ-H)(μ-P(cyclo-C6H11)2)(CO)6(μ4-P(cyclo-C6H11))
  参考文献：
  名称：

  Vierkernige Clusterkomplexe vom Typ [MM′(AuPR3)2(μ-H)(μ-PCy2)(μ4-PCy)(CO)6] (M, M′ = Mn, Re; R = Ph, Cy, Et): Synthese, Struktur und Topomerisierung

  摘要：

  The dirhenium complex [Re-2(mu -H)(mu -PCy2)-(CO)(7)(ax-H2PCy)] (1) reacts at room temperature in thf solution with each two equivalents of the base DBU and of ClAuPR3 (R = Ph, Cy, Et) in a photochemical reaction process to afford the tetranuclear clusters [Re-2(AuPR3)(2)(mu -H)(mu -PCy2)(mu (4)-PCy)(CO)(6)] (R = Ph (2), Cy (3), Et (4)) in yields of 35-48%. The homologue [Mn-2(mu -H)(mu -PCy2)(CO)(7)(ax-H2PCy)] (5) leads under the same reaction conditions to the corresponding products [Mn-2(AuPR3)(2)(mu -H)(mu -PCy2)(mu (4)-PCy)(CO)(6)] (R = Ph (6), Et (8)). Also [MnRe(mu -H)(mu -PCy2)(CO)(7)(ax/eq-H2PCy)] (9) reacts under formation of [MnRe(AuPR3)(2)(mu -H)(mu -PCy2)(mu (4)-PCy)(CO)(6)](R = Ph (10), Et (11)). All new cluster complexes were identified by means of H-1-NMR, P-31-NMR and nu (CO)-IR spectroscopic measurements. 2, 4 and 10 have also been characterized by single crystal X-ray structure analyses with crystal parameters: 2 triclinic, space group P (1) over bar, a = 12.256(4) Angstrom, b = 12.326(4) Angstrom, c = 24.200(6) Angstrom, alpha = 83.77(2)degrees, beta = 78.43(2)degrees, gamma = 68.76(2)degrees, Z = 2; 4 monoclinic, space group C2/c, a = 12.851(3) Angstrom, b = 18.369(3) Angstrom, c = 40.966(8) Angstrom, beta = 94.22(1)degrees, Z = 8; 10 triclinic, space group P (1) over bar, a = 12.083(i) Angstrom, b = 12.185(2) Angstrom, c = 24.017(6) Angstrom, alpha = 83.49(29)degrees, beta = 78.54(2)degrees, gamma = 69.15(2)degrees, Z = 2. The trapezoid arrangement of the metal atoms in 2 and 4 show in the solid structure trans-positioned an open and a closed Re . . . Au edge. In solution these edges are equivalent and, on the P-31 NMR time scale, represent two fluxional Re-Au bonds in the course of a topomerization process. Corresponding dynamic properties were observed for the dimanganese compounds 6 and 8 but not for the related MnRe clusters 10 and 11. 2 and 4 are the first examples of cluster compounds with a permanent Re-Au bond valence isomerization.

  DOI：

  10.1002/1521-3749(200011)626:11<2293::aid-zaac2293>3.0.co;2-f
• 作为产物：
  描述：

  Mn2(μ-H)(μ-P(cyclo-C6H11)2)(CO)8 、 环已基膦 在 Me₃NO 作用下， 以 四氢呋喃 为溶剂， 以98%的产率得到Mn2(μ-H)(μ-P(cyclo-C6H11)2)(CO)7(ax-H2P(cyclo-C6H11))
  参考文献：
  名称：

  Vierkernige Clusterkomplexe vom Typ [MM′(AuPR3)2(μ-H)(μ-PCy2)(μ4-PCy)(CO)6] (M, M′ = Mn, Re; R = Ph, Cy, Et): Synthese, Struktur und Topomerisierung

  摘要：

  The dirhenium complex [Re-2(mu -H)(mu -PCy2)-(CO)(7)(ax-H2PCy)] (1) reacts at room temperature in thf solution with each two equivalents of the base DBU and of ClAuPR3 (R = Ph, Cy, Et) in a photochemical reaction process to afford the tetranuclear clusters [Re-2(AuPR3)(2)(mu -H)(mu -PCy2)(mu (4)-PCy)(CO)(6)] (R = Ph (2), Cy (3), Et (4)) in yields of 35-48%. The homologue [Mn-2(mu -H)(mu -PCy2)(CO)(7)(ax-H2PCy)] (5) leads under the same reaction conditions to the corresponding products [Mn-2(AuPR3)(2)(mu -H)(mu -PCy2)(mu (4)-PCy)(CO)(6)] (R = Ph (6), Et (8)). Also [MnRe(mu -H)(mu -PCy2)(CO)(7)(ax/eq-H2PCy)] (9) reacts under formation of [MnRe(AuPR3)(2)(mu -H)(mu -PCy2)(mu (4)-PCy)(CO)(6)](R = Ph (10), Et (11)). All new cluster complexes were identified by means of H-1-NMR, P-31-NMR and nu (CO)-IR spectroscopic measurements. 2, 4 and 10 have also been characterized by single crystal X-ray structure analyses with crystal parameters: 2 triclinic, space group P (1) over bar, a = 12.256(4) Angstrom, b = 12.326(4) Angstrom, c = 24.200(6) Angstrom, alpha = 83.77(2)degrees, beta = 78.43(2)degrees, gamma = 68.76(2)degrees, Z = 2; 4 monoclinic, space group C2/c, a = 12.851(3) Angstrom, b = 18.369(3) Angstrom, c = 40.966(8) Angstrom, beta = 94.22(1)degrees, Z = 8; 10 triclinic, space group P (1) over bar, a = 12.083(i) Angstrom, b = 12.185(2) Angstrom, c = 24.017(6) Angstrom, alpha = 83.49(29)degrees, beta = 78.54(2)degrees, gamma = 69.15(2)degrees, Z = 2. The trapezoid arrangement of the metal atoms in 2 and 4 show in the solid structure trans-positioned an open and a closed Re . . . Au edge. In solution these edges are equivalent and, on the P-31 NMR time scale, represent two fluxional Re-Au bonds in the course of a topomerization process. Corresponding dynamic properties were observed for the dimanganese compounds 6 and 8 but not for the related MnRe clusters 10 and 11. 2 and 4 are the first examples of cluster compounds with a permanent Re-Au bond valence isomerization.

  DOI：

  10.1002/1521-3749(200011)626:11<2293::aid-zaac2293>3.0.co;2-f