ساختار بلوری کمپلکس(٢،'٢- بی پیریدین) (۲ ،۵ – دی کلروفنیل سیانامیدو) (۲ ،'٢:'۶،"۲-ترپیریدین) رودیم(III) هگزافلوئوروفسفات [Rh(terpy)(bpy)(2,5-Cl2pcyd)](PF6)2.0.5CH3CN

نویسندگان

دانشگاه سیستان و بلوچستان

چکیده

نخستین ساختار بلوری کمپلکس فنیل سیانامید رودیم (III) با فرمول [Rh(terpy) (bpy) (2,5-Cl2pcyd)] (PF6)2 گزارش شده است. بلورهای [Rh(terpy)(bpy)(2,5-Cl2pcyd)] (PF6)2 .0.5CH3CN به وسیله نفوذ اتر به داخل محلول استونیتریلی کمپلکس رشد داده شد. داده­های ساختار بلوری به صورت زیر می­باشد: سیستم تبلور از نوع­ اورتورومبیک و گروه فضائی Fdd2 است.

a = 84.228(3), b = 8.7162(3), c = 21.4921(7)Å, V=15778.4(9) Å3, and Z=16.

ساختار بر اساس4971 انعکاس مستقل باI>2σ(I)   ، R = 0.0644 و Rw=0.1752 به دست آمد. ORTEP < /span> مربوط به کمپلکس[Rh(terpy)(bpy)(2,5-Cl2pcyd)](PF6)2 .0.5CH3CN  نشان می­دهد که سه حلقه پیریدیلی لیگاند ترپیریدین و دو حلقه لیگاند بی­پیریدین به وسیله اتمهای نیتروژن خود به رودیم(III) کوئوردینه شده­اند. گروه آنیونی سیانامید به صورت انتهائی و به وسیله نیتروژن نیتریلی خود به یون رودیم(III) کوئوردینه شده است. پیوند RhIII –NCN خمیده و زاویه آن ° 4/125 است.

کلیدواژه‌ها


عنوان مقاله [English]

Crystal Structure of ( 2,2′-bipyridine) ( 2,5-dichlorophenylcyanamido) (2,2΄:6′,2″–terpyridine)rhodium(III) Hexafluorophosphate, [Rh(terpy)(bpy)(2,5-Cl2pcyd)](PF6)2.0.5CH3CN

چکیده [English]

The first crystal structure of a phenylcyanamide Rh(III) complex, [Rh(terpy)(bpy)(2,5-Cl2pcyd)](PF6)2 (terpy = 2,2΄:6′,2″– terpyridine, bpy= 2,2΄-bipyridine, and 2,5-Cl2pcyd = 2,5-dichlorophenylcyanamide) has been reported in this paper. Crystals of [Rh(terpy)(bpy)(2,5-Cl2pcyd)](PF6)2 .0.5CH3CN were grown by ether diffusion into an acetonitrile solution of the complex. Crystal structure data: orthorhombic system, space group Fdd2, with a = 84.228(3), b = 8.7162(3), c = 21.4921(7)Å, V=15778.4(9) Å3, and Z=16. The structure was refined by using 4971 independent reflections with I>2σ(I) to a R factor of 0.0644 and Rw = 0.1752. ORTEP drawing of [Rh(terpy)(bpy)(2,5-Cl2pcyd)](PF6)2 .0.5CH3CN shows that the terpy and bpy ligands are coordinated to the RhIII through their nitrogen atoms in a mutually perpendicular fashion. The anionic cyanamide group is coordinated end-on by the nitrile nitrogen to the RhIII. The RhIII –NCN bond is bent, having an angle of 125.4o. This bent bond is largely determined by the σ-bonding interaction of a cyanamide non-bonding electron pair in a sp < sup>2 hybrid orbital.

کلیدواژه‌ها [English]

  • Phenylcyanamide Ligands
  • Rhodium (III) Complex
  • Pyridyl Ring
  • Bipyridine
  • Terpyridine
[1] Crutchley R. J., "Phenylcyanamide ligands and their metal complexes", Coord. Chem. Rev. 219-221 (2001) 125-155.

[2] Kabesova M., Boca R., Melnick M., Valigura D., Dunaj-jurco M., "Boding properties of thiocyanate groups in copper(II) complexes", Coord. Chem. Rev. 140 (1995) 115-135.

[3] Naklicki M. L., Crutchley R. J., "Coordination chemistry of neutral phenylcyanamide ligands bound to pentaammineruthenium(II)", Inorg. Chem. 28 (1989) 4226-4229.

[4] Crutchley R. J., Nakliki M. L., "Pentaammineruthenium (III) complexes of neutral and anionic (2,3-dichlorophenyl) cyanamide: spectroscopic analysis of ligand to metal gharge transfer", Inorg. Chem. 28 (1989) 1955-1958.

[5] Buchanan G. W., Crutchley R. J.,"15 N-NMR study of phenylcyanamides",

Magn. Reson. Chem. 32 (1994) 552-258.

[6] Chisholm M. H., Folting K., Huffman J. C., Marchant N. S., "Notable features in the molecular structure of W2(OCH2-t-Bu)6(NCNMe2)3, Polyhedron", 3 (1984) 1033-1035.

[7] Rezvani A. R., Evans C. E. B., Crutchley R. J., "strong metal-metal coupling in a dinuclear (terpyridine) ruthenium mixed – valence complex incorporating the bridging ligand 1,4- dicyanamidobenzene dianion", Inorg. Chem. 34 (1995) 4600-4604.

[8] Rezvani A. R., Bensimon C., Cromp B., Reber C., Greedan J. E., Kodratiev V. V., Crutchley R. J., "Inner coordination sphere control of metal-metal superexchange in ruthenium dimmers", Inorg. Chem. 36 (1997) 3322-3329.

[9] Rezvani A. R., Crutchley R. J., "Dependence of the Ru(III)-cyanamide

chromophore on inner-spehere coordination: comparison of cis-[Ru(bpy)2

(pcyd)2]+and [Ru(NH3)5(pcyd)]2+complexes", Inorg.hem. 33 (1994) 170-174.

[10] Rezvani A. R., Evans C. E. B., Naklicki M. L., White C. A., Kondratiev V. V., Crutchley R. J., "An investigation of superexchange in dinuclear mixed-valence ruthenium complexes", J. Am. Chem. Soc. 120 (1998) 13096-13103.

[11] Mosher P. J., Yap G. P. A., Crutchley R. J., "Influuence of the inner coordination sphere on the Ru(II)-cyanamide ligand – to – metal charge transfer chromophore", Inorg. Chem. 40 (2001) 550-553.

[12] Brader M. L., Ainscough E. W., Backer E. N., Brodie A. M., Ingham S.L., "Synthetic, spectroscopic, and X-ray crystallographic studies on phenylcyanamidocopper (II) complexes. The characterization of three different co-ordination modes for phenylcyanamide anions", J. Chem. Soc. Dalton Trans. (1990) 2785-2792.

[13] Aquino M. A. S., Crutchley R.J., Lee F.L., Gabe E.J., Bensimon C., "Structure of 1,4- benzenedicyanamide dianion derivatives, Acta Crystallogr", C49 (1993) 1543-1547.

[14] Evans C. E. B., Yap G. P. A., Crutchley R. J., "Comparison of hole transfer superexchange in dinuclear mixed-valence ruthenium complexes", Inorg. Chem. 37 (1998) 6161-6167.

[15] Hadadzadeh H., Rezvani A. R., "The electrochemical and spectroscopic studies of trans- [Co((DO)(DOH)pn)LL’] complexes", Iran J. Chem. & Chem. Eng. 21 (2002) 21-27.

[16] Nakliki M. L., White C. A., Kondratiev V. V., Crutchley R. J., "Mono and dinuclear ruthenium(III) and ruthenium(IV) complexes of 1,4-dicyanamido –5-dimethylbenzene dianion", Inorg. Chim. Acta, 242 (1996) 63-69.

[17] Desjardins P., Yap G.P.A., Crutchley R.J., "tetrakis(pyridine)ruthenium trans complexes of phenylcyanamide ligands", Inorg. Chem. 38 (1999) 5901-5905.

[18] Aquino M. A. S., Crutchley R. J., "A pentaamineruthenium mixed-valence complex with 1,4-dicyanamidobenzene dianion as bridging ligand", Inorg. Chem. 29 (1990) 3641-3644.

[19] Letcher R. J., Zhang W., Bensimon C., Crutchley R. J., "1,3-Bis(2’- pyridylamino)isoindolinato)nickel (II) complexes of phenylcyanamido ligands", Inorg. Chim. Acta 210 (1993) 183-191.

[20] Zhang W., Bensimon C., Crutchley R. J., "(Terpyridine)palladium(II) complexes of phenylcyanamide ligands", Inorg. Chem. 32 (1993) 5808-5812.

[21] Brader M. L., Aniscough E. W., Baker E. N., Brodie A. M.," Copper(II) promoted desulphurization of N-phenylthiourea", Polyhedron 8 (1989) 2219-

2221.

[22] Hadadzadeh H., Rezvani A. R., Patrick B., "Stucture and spectroscopic studies of cis-bis(bipyridine) cobalt (III) complexes of phenylcyanamide ligands", Inorg. Chim. Acta 336 (2002) 125-130.

[23] Derosa M. C., Crutchley R. J., "Semiconductor properties in an iodine-doped Pt(II) dinuclear complex", Inorg. Chem. 40 (2001) 1406-1407.

[24] Ainscough E. W., Backer E. N., Brader M. L., Brodie A. M., Ingham S.L.,Waters J. M., Hanna J. V., Healy P. C., "Synthetic, spectroscopic and X-ray crystallographic studies on phenylcyanamidocopper(I) complexes", J. Chem. Soc. Dalton Trans.(1991) 1243-1250.

[25] Kim M. Y., Seok W. K., Dong Y., Yun H., "Crystal structure and electrochemical behavior of Rh polypyridyl complexes", Inorg. Chim. Acta 319 (2001) 194-198.

[26] SAINT Release 6.06,"Integration Software for Single Crystal Data", Bruker AXS Inc., Madison (1999).

[27] Sheldrick G. M., SADABS, "Bruker Area Detector Absorption Corrections", Bruker AXS Inc., Madison (1996).

[28] SHELXTL Release 5.10, "The Complete Software Package for Single Crystal Structure Determination", Bruker AXS Inc., Madison, (1997).

[29] Sheldrick G. M., "SHELXS97, Program for Crystal Structure Solution", University of Göttingen, Germany (1997).

[30] Sheldrick G. M., "SHELXL97, Program for Crystal Structure refinement", University of Göttingen, Germany (1997).

[31] Spek A. L., "PLATON, Molecular Geometry Program", University of Utrecht, Utrecht, Holland (2000).