Oxidative scission of a Mo-Mo quadruple bond.

نویسندگان

  • F A Cotton
  • C A Murillo
  • H C Zhou
چکیده

Two compounds containing the cations Mo2(DPhIP)4n+, n = 1 or 2 and DPhIP = the anion of 2,6-diphenyliminopiperidine, have been obtained by oxidation of the quadruply-bonded Mo2(DPhIP)4 species. The first oxidation process conserves the structure but results in a slight increase of the Mo-Mo distance from 2.114(1) to 2.136(2) A in [Mo2(DPhIP)4](PF6).2CH2Cl2 (1.2CH2Cl2). However, the second oxidation process breaks the dimolybdenum bond, giving a bioctahedral complex, [Mo2(DPhIP)4](BF4)2.5CH3CN.Et2O (2.5CH3CN.Et2O), with Mo...Mo separation of 2.9954(7) A. Crystallographic data for 1.2CH2Cl2 are space group C2/c, a = 17.1891(9) A, b = 17.807(1) A, c = 24.210(2) A, beta = 106.403(4) degrees, Z = 4; for 2.5CH3CN.Et2O, space group P2(1)/n, a = 16.523(5) A, b = 27.418(5) A, c = 18.163(3) A, beta = 93.48(2) degrees, Z = 4.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

By Cleavage of the Quadruple Bond in Mo , ( 0 , Ccf

Addition of an excess of t-butyl isocyanide to solid Mo2 (0, CCF3 )4 or MO?_ (0, CMe)4 gives (t-BuNC), Mo(Oz CCF3 )* or (t-BuNC), Mo(Oz CMe), , respectively. The quadruple bond in K4 MO* Cl8 or Cl4 MO, (n-Bus P)4 also can be cleaved by an excess of t-butyl isocyanide to yield (t-BuNC), MoCl, _ The anionic ligands can be exchanged with ammonium hexafluorophosphate in presence of excess t-BuNC to...

متن کامل

Journey from Mo-Mo quadruple bonds to quintuple bonds.

Heating K(4)Mo(2)Cl(8) and 2 equiv of Li[RC(NDipp)(2)] (R = H, Ph; Dipp = 2,6-i-Pr(2)C(6)H(3)) in tetrahydrofuran (THF) at 60 degrees C gives two paddlewheel type quadruply bonded dimolybdenum complexes, Mo(2)(mu-Cl)[Cl(2)Li(OEt(2))][mu-eta(2)-RC(N-2,6-i-Pr(2)C(6)H(3))(2)](2) (R = H (1), Ph (2)). The Mo-Mo bond lengths of 1 and 2 are 2.0875(4) and 2.0756(8) A, respectively, indicating typical M...

متن کامل

A three-coordinate and quadruply bonded Mo-Mo complex.

Reaction of MoCl3(THF)3 with [Me2Si{NLi(Dipp)}2]2 (Dipp = 2,6-i-PrC6H3) afforded a triply bonded dimolybdenum complex 1,2-Mo2Cl2[Me2Si(NDipp)2]2 1, spanned by two Me2Si[N(Dipp)]2 ligands, thus resulting in a syn conformation. The air- and moisture-sensitive compound 1 was characterized by NMR spectroscopic, elemental, and single-crystal X-ray crystallographic analysis. Reduction of 1 by Na/Hg y...

متن کامل

Reaction of Binuclear Carboxylate Complexes of Molybdenum, Rhenium, Ruthenium, and Rhodium with tert-Butyl Isocyanide: Metal-Metal Bond Cleavage vs. Bond Retention

terr-Butyl isocyanide cleaves the quadruple metal-metal bonds in Moz(02CMe),, MoZ(OzCCF3),, or K,MozCls to give the mononuclear, seven-coordinate species MO(?-BUNC)~(O~CM~)~ or [Mo(t-B~Nc)~x] [XI, where X is OZCCF3 or C1. These diamagnetic, 18-electron complexes may be converted into the known binary dication [Mo(t-BuNC),] [PF,], by action of NH4PF6 and excess r-BuNC or into the polyoxoanion co...

متن کامل

trans-Di-μ-acetato-[μ-N,N-bis­(diphenyl­phosphino)aniline]bis­[chlorido­molybdenum(II)](Mo—Mo)–dichloro­methane–tetra­hydro­furan (1/0.3/1.7)

The mol-ecular structure of the title compound, [Mo(2)(CH(3)COO)(2)Cl(2)(C(30)H(25)NP(2))]·0.3CH(2)Cl(2)·1.7C(4)H(8)O, features an Mo-Mo dumbbell bridged by two acetate groups which are trans to each other. Perpendicular to the plane spanned by the acetate groups, the Ph(2)PN(Ph)PPh(2) ligand bridges both Mo atoms, having a P-N-P angle of 114.09 (19)°. In a trans position to the PNP ligand are ...

متن کامل

ذخیره در منابع من

ذخیره در منابع من قبلا به منابع من ذحیره شده

{@ msg_add @}


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Inorganic chemistry

دوره 39 15  شماره 

صفحات  -

تاریخ انتشار 2000