close

Вход

Забыли?

вход по аккаунту

?

Preparation Ligand Exchange Reactions and Structure of a Diene(aqua)ruthenium Complex [(cod)Ru(H2O)4](OTs)2.

код для вставкиСкачать
The formation of bis(phosphino)nitrilimine 3 demonstrates the potential of tin diazo compounds as nitrilimines
precursors and allows a clarification of the mechanism of the
reaction of electrophiles with lithium diazo compounds. The
first experimental evidence of an organic nitrilimine and its
isolation were separated by 30 years. The crucial step was the
stabilization of these 1,3-dipoles by heteroatom substituents.
Experimental Procedure
6: An acetonitrile solution (4 mL) of bis(trimethylstanny1)diazomethane (2)
(278mg, 0.757mmol) was added dropwise to 2 equivalents of triphenylmethylchloride (421 mg, 1.51 mmol) in acetonitrile (6 mL) at - 30 "C. The solution was stirred for 1 h at - 30 "C, and 6 precipitated as a pale yellow solid
which was washed several times with acetonitrile. Trimethylchlorostannane was
removed under vacuum (ca. 15 h) at room temperature. Nitrilimine 6 was recrystallized from THF/Et,O (358 mg, 90%). Nitrilimine 6 is air stable in the
solid state but slowly decomposes in solution above -20 "C.
Cycloaddition reactions: A solution of the dipolarophile in T HF was added to
the stoichiometric amount of nitrilimine 6 in T HF at - 30 "C. The mixture was
allowed to warm to room temperature, and the solvent was then removed at
lo-, Torr. The solids 7-10 were washed several times with pentane and dried
in vacuo.
Received: September 30, 1991 [Z 4940 IE]
German version: Angew. Chem. 1992, 104, 481
CAS Registry numbers:
1,56183-63-2; 2,21803-09-8; 3,137320-40-2; 4,113533-26-9; 5,105309-80-6; 6,
139130-94-2;7, 139130-95-3;8, 139136-96-4;9,139130-97-5; 10, 139130-98-6;
methyl acrylate, 96-33-3; methyl propiolate, 922-67-8; dimethyl fumarate, 62449-7; dimethyl maleate, 624-48-6; triphenylmethylchlorid, 76-83-5.
[I] M. Regitz, Angew. Chem. 1991,103,691 -693; Angew. Chem. In!. Ed. Engl.
1991,30, 674-676.
[2] a) A. Igau, H. Grutzmacher, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc.
1988, 110, 6463-6466; b)A. Igau, A. Baceiredo, G. Trinquier, G.
Bertrand, Angew. Chem. 1989, 10f, 617-618; Angew. Chem. In!. Ed. Engl.
1989,28,621-622; c) G. R. Gillette, A. Baceiredo, G. Bertrand, ibid. 1990,
102, 1486-1488 and 1990,29, 1429-1431.
131 A. J. Arduengo, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113,
361-363.
[4] a) M. P. Arthur, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc. 1991,113,
5062-5063; b) F. Castan, A. Baceiredo, G. Bertrand, Angew. Chem. 1989,
101,1253-1254; Angew. Chem. Int. Ed. Engl. 1989,28, 1250-1251; c) F.
Castan, A. Baceiredo, D. Bigg, G. Bertrand, .
I
Org. Chem. 1991,56, 1801
1807; d) M. Granier, A. Baceiredo, Y Dartiguenave, M. Dartiguenave,
M. J. Menu, G. Bertrand, 1 Am. Chem. Soc. 1990,112,6277-6285,
[5] M. Regitz, G. Mass, Diazo Compounds, Properties and Synthesis, Academic Press, London, 1986.
[6] a) M. Granier, A. Baceiredo, G. Bertrand, Angew. Chem. 1988,100,13971398; Angew. Chem. I n f . Ed. Engl. 1988,27, 1350-1351; b) C. Wentrup,
Heiv.Chim. Acta 1978, 61, 1755-1764; c) R. Gleiter, W Rettig, C. Wentrup, ihid. 1974, 57, 2111-2124; d)A. Padwa, T. Caruso, s. Nahm, A.
Rodrigez, J. Am. Chem. Soc. 1982, 104. 2865-2871.
[7] a) J. Lorberth, S. H. Shin, H. Donath, S. Wocadlo, W. Massa, J.
Organornet. Chem. 1991, 407, 167-171; b)A. Fadini, E. Glozbach, P.
Krommes, J. Lorberth, ibid. 1978, 149, 297-307.
[8] M. F. Lappert, J. Lorberth, J. S. Poland, J. Chem. Soc. A 1970,2954-2959.
[9] Selected spectroscopic data: 3: "P NMR (THF): 6 = 96.0, 45.5 [d,
4J( 3 1 P, "P) = 9 Hz]; "CNMR
(C,D,): 6 = 63.3 [d, 'J(,'P, I3C) =
available on request from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH, D-W-7514
Eggenstein-Leopoldshafen 2, on quoting the depository number CDS56010, the names of the authors, and the journal citation.
[13] a) P. Caramella, K. N. Houk, 1 Am. Chem. Soc. 1976, 98, 6397-6399;
b) P. Caramella, R. W. Gandour, J. A. Hall, C. G. Deville, K. N. Houk,
ibid. 1977, 99, 385-392, and references therein.
[14] a) R. Huisgen, Angew. Chem. 1963, 75, 604-637 and 742-754; Angew.
Chem. Int. Ed. Engl. 1%3,2, 565-608 and 633-645; b) P. Caramella, P.
Grunanger in 1.3Dipolar Cycloaddition Chemistry (Ed.: A. Padwa), Wiley,
New York, 1984; c) R. Huisgen, M. Seidel, G. Wallbillich, H. Knupfer,
Tetrahedron 1962, 17, 3-29; d) A. Eckell, R. Huisgen, R. Sustmann, G.
Wallbillich, D. Grashey, E. Spindler, Chem. Ber. 1967, 100. 2192-2213.
Preparation, Ligand Exchange Reactions, and
Structure of a Diene(aqua)ruthenium Complex
I(COd)RU(H*O),l(OTS), **
By Ulrich Kolle,* Gabriele Flunkert, R a y Gorissen,
Martin U . Schmidt, and Ulli Englert
Metal ions which together with water are complexed to
arenes or olefins, contradict the Jerrgensen rule['] for transition metal complexes (either hard, hard or soft, soft!) and
therefore are expected to have special properties. Apart from
the well characterized dicationic benzene(aqua)Ru- and 0 s
complexes". 31 as well as the recently described tetramethylthiophene-Ru analogue,L4] a series of dicationic cyclopentadienyl(aquaEmeta1 complexes, some of them less well characterized, of the type [Cp(*)M(H,0)3]2+(Cp* = $-C,Me,)
is known; [CpCr(H,0)3]2+,[s1 [ C ~ * C O ( H , O ) ~ ] ~ + , [ ~ *
[Cp*Rh(H,0),]2+,[7981[ C ~ * R U ( H , O ) , ] ~ +These
. [ ~ ~ complexes are of differing stabilities. Most recently also a number of olefin(aqua) complexes was prepared.
The dication 1 of the title compound proved to be a surprisingly robust organometallic aqua complex which was
prepared in the way shown in Scheme 1 and is the first structurally characterized diene(aquakmeta1 complex.
-
62.5 Hz, CNN]; I4NNMR (CDCI,): 6 = -191.9 (CAW); IR (THF):
v = 2047 cm-'(CNN). 7: 13C NMR (CDCI,): b = 42.2 (CH,), 62.8 (CH),
156.5 (CN); 'H NMR (CDCI,): 6 = 2.2 [dd, J = 16.8, 11.4 Hz, 1 H, CH,),
2.6(dd, J=16.8, 9.3 Hz, lH,CH,], 3.9 [dd,3=11.4,9.3 Hz, lH,CH]. 8:
13C NMR(CDC1,): 6 = 115.1 (CH), 134.6 (CCO,), 155.1 (CN); 'H NMR
(CDCI,): 6 = 6.5 (s, 1 H, CH). 9: 13CNMR (CDCI,): 6 = 59.8 (CCH),
67.7 (NCH), 150.5 (CN); 'H NMR (CDCI,): 6 = 4.1 [d, J = 11.4 Hz, 1H,
CCH], 4.3 [d, J =11.4 Hz, 1 H, NCH]. 10: 13C NMR (CDCI,): 6 = 57.5
(CCH), 67.6 (NCH), 155.6 (CN); 'H NMR (CDCI,): 6 = 3.5 [d,
J = 1 0 . 4 H ~ lH,CCH],4.2
,
[d, J =10, 4Hz , lH, NCH].
[lo] a) A. Baceiredo, A. Igau, G. Bertrand, M. J. Menu, Y. Dartiguenave, M.
Dartiguenave, J. J. Bonnet, 1 Am. Chem. Soc. 1986, 108, 7868-7869;
b) M. J. Menu, M. Dartiguenave, Y Dartiguenave, J. J. Bonnet, G.
Bertrand, A. Baceiredo, J. Organornet. Chem. 1989, 372, 201-206.
(111 K. Horchler von Locquenghien, R. Reau, G. Bertrand, J. Chem. Soc.
Chem. Commun., 1991, 1192-1193.
[12] Space group P 2 , / c , a = 17.793(2), b =10.635(1), c = 17.013(2)A, j3 =
102.41(1)", V = 3144.1 A3, 2 = 4, 6343 measured reflections, 3165 inde> 3 u ( e ) ] ,404 retined parameters, R(F,) = 0.027
pendent observed
( R , = 0.029). Further details of the crystal structure investigations are
[e
440
0 VCH
krlagsgesellschafi mbH, W-6940 Weinheim, 1992
2
Scheme 1. Counterions of the dicationic complexes: p-CH,C,H,SO,
or SO:-. cod = 1,5-cyclooctadiene.
1
(OTs)
The photochemical route convenient for the preparation
of [Ru(H,O),I2+ (2),['. lo]avoids the somewhat involved reduction of aqueous ruthenic acid by activated lead["] and
makes smaller scale preparations of the hexaaqua-metal ion
easier. In contrast to the reaction of 2-(OTs), with 1,3-cyclooctadiene which gave a (f'-cyclooctadienyl)(q6-arene)
complex,['21we found that in ethanol with cod only a complexation to the dicationic complex 1 with one cod and four
aqua ligands occurred (yields and physical data for this and
[*I
[**I
Prof. Dr. U. Kolle, Dipl.-Chem. G. Flunkert, Dip1.-Chem. R. Gorissen,
DipLChem M. Schmidt, Dr. U. Englert
Institut fur Anorganische Chemie der Technischen Hochschule
Professor-Pirlet-Strasse 1, D-W-5100 Aachen (FRG)
This work was supported by the Fonds der Chemischen Industrie. We
thank Prof. H. Elias, Institut fur Anorganische Chemie der Technischen
Hochschule Darmstadt, for the ligand H,salen and Johnson Matthey,
Reading, England for the loan of RuCI,.
0570-0833/92/0404-0440X 3.50+ ,2510
Angew. Chem. Int. Ed. Engl. 31 (1992) No. 4
the other newly prepared compounds see Table 1). This is,
dependent on the anion, soluble in polar organic solvents
and particularly soluble in water. In contrast to 2, the solutions are not air sensitive and also do not decompose or
disproportionate when warmed.[13]
Table 1. Yields and selected physical data of the compounds 1-(OTs),, 3, 4,
S a - 5 c (as PF, salt), and 6-(0Ts),.
I-(OTs),: 'H NMR (80 MHz, D,O, H,O (6 = 4.65) as standard): 6 = 4.4 (br s,
4 H ; =CH), 2.3 (br s, 8 H ; CH,); "CNMR (D,O): 6 = 28.86 (t, J(C,
H) =132.6Hz). 89.90 (d, J(C, H) =161.6 Hz); IR(KBr) V [cm-'1 = 3271 (br,
HZO), 2960, 2930, 2880 (CH,, CH,), 1635 (C=C), 1446 (6 CH,) 682 (6
HC=CH), correct C,H-analysis
3: Yield 80%; ' H N M R (300 MHz, C,D,): 6 =1.75, 2.01 (s, each 3 H ; CH,),
5.25 (s, 2 H ; CH), 1.83, 2.44 (m, each 2H), 2.16 (m, 4 H ; CH,), 4.23, 4.57 (m,
each 2 H ; =CHI; "CC('H) NMR (60.2 MHz, C,D,): 6 = 27.38,28.12 (CH,),
98.77 (CH), 186.67, 186.75 (C-O), 28.86, 30.78 (CH,), 88.99, 92.08 (=CH) [a]
4: ' H N M R (SOMHz, CD,OD): 6 = 3.95 (s, 4 H ; CH,), 6.9, 7.2 (m, 8 H ;
arom.), 8.44 (2H=CH), ca. 2 (br m, 8 H ; CH,), ca. 5.6 (br m, 4 H ; =CH)
5a-PF6: Yield quantitative; 'H NMR (80 MHz, CDCI,): 6 = 5.03 (s, 5H; Cp),
ca. 4 (br m. 12H, OCH,; 4H, CH), 3.06 (br s, 2 H ; H,O), ca. 2.1 (m, 8 H ; CH,),
1.22, 1.27, 1.28 (t. J = 7 . 1 Hz, each 3 H ; CH,); IR (KBr) i[cm-'] =128Os
(P=O). 1112, 1037s (6 POEt), 839 vs (PF,)
5b-PF6: from 5 a and NaN,, yield 70%; ' H N M R (SOMHz, CD,OD):
6 = 4.15 (s. 5 H ; Cp), ca. 4.1 (br m, 12H, OCH,; 4H, CH), ca. 2.14 (m, 8 H ;
CH,), 1.32 (t, J = 7 Hz, 6 H ; CH,), 1.27 (t, J = 7 Hz, 3 H ; CH,); IR (KBr)
i[cm-'] = 2060s(N,), 1112. 1140s(6P(O)OEt)
Sc-PF, from 5a-PF, and KSCN; 'HNMR almost like 5b-PF6; IR (KBr)
i. [cm-'1 = 2126, 2077s (SCN), 1113, 1040s (6 P(0)OEt)
6-(OTs),. from 1-(OTs), with 2 b a r CO, 20 h, roomtemp., H,O; 'HNMR
(80 MHz, D,O): 6 = 4.40 (br s, 4 H ; =CH), 2.08 (s, 8 H ; CH,), 2.31 (s, 6 H ;
CH,OTs), 7.68, 7.57, 7.33, 7.23 (m. 8 H ; arom.); ',CNMR (CD,OD): 6 =
197.5 (br s, CO), 94 (m, =CH), ca. 30 (m, CH,); IR (KBr) i[cm-'] =
1984cm-' (CO)
equal intensity. The remaining aqua ligand can be easily
exchanged for other ligands to form a variety of further
complexes 5.
According to the NMR spectra, the salene in 4 coordinates in a similar way to acac in 3 such that a molecule with
C, symmetry results. Particularly noteworthy is the exchange of an aqua ligand for CO under a mild CO pressure.
This reaction corresponds to the recently found carbonylation of 2-(OTs), which afforded the monocarbonyl(aqua)
complex.[151Here, too, the splitting of the cod signals, especially in the 13CNMR spectrum, indicates an unsymmetrical
molecular unit and thus, together with the single CO absorption in the IR spectrum, a monocarbonyl complex. With
halide ions, for example Br-, the polymeric dihalide
[ (cod)RuBr,], immediately precipitates from water. Neither
this, nor the analogous chloride could be used, for example
with Ag+ ions in water, to form 1.
Crystals of I-(OTs), suitable for a structure determination
were obtained by slow evaporation of an aqueous acetone
solution. The molecular structure of 1 is shown in Figure 1,
and a packing diagram of 1-(OTs), in Figure 2. The complex
[a] See also P. Powell, .
I
Organomel. Chem. 1974, 65, 89 [6]
In the cyclic voltammogram in dimethylformamide, within the limits + 1.9 to ca. - 1.2 V (saturated calomel electrode), no electon transfer is observed.
Compound 1 was chemically characterized by ligand
exchange reactions, which led to the complexes 3-7
(Scheme 2). During these reactions, depending on the ligand,
one to four aqua ligands were exchanged. The tripod ligand
served as a model for a triaqua ligand moiety.[14]The coordination shown in 5, to a metal complex fragment with twofold symmetry (see Fig. 3), causes the methyl signals of the
OEt groups of the tripod ligand to split into three triplets of
p&&
Sa.L=H,O
5b,L=N,
Sc.L=NCS
4
&O
Scheme 2. R = OEt. Hacac = acetylacetone, H,salen
enediamiue. a): EtOH, K,CO,, 4 0 T , 2h.
Angew. Chrm. Inl. Ed. Engl. 31 (1992) No. 4
= bis(salicyhdene)ethyl-
0 VCH
Fig. 1. Crystal structure of 1 (SCHAKAL). Distances [A]: Ru-01 2.158(1),
Ru-02 2.095(2), Ru-C1 2.178(1), C1-Cl' 1.367(3); Angles ["I: 01-Ru-01'
86.14(9), 02-Ru-02' 154.8(1), (middle C1-C1')-Ru-cis-01 93.82, (middle C1Cl')-Ru-rrans-Ol 180, (middle Cl-Cl')-Ru-02 99.15, (middle C1-C1')-Ru(middle Cl"-Cl"') 86.22.
Fig. 2. Packing diagram of I-(OTs),. Oxygen atoms dark. The strands of
[(cod)R~(H,0),]~+
ions, each twice H-bonded via tosylate ions, lie along the c
axis, distance RuO...H...OS 2.746(2), 2.683(2) A.
contains one (cod)Ru unit, to which are symmetrically coordinated four aqua ligands to yield a highly distorted octahedral arrangement. Two crystallographic mirror planes of the
space group Pmmn through the Ru, interconvert the two
aqua ligand sets as well as the cod halves. Of the aqua lig-
Verlagsgesellschaft mbH. W-6940 Weinheim, 1992
0S70-0833/92/0404-0441$3.50+ .2S/0
441
Experimental Procedure
A solution of [Ru(H,O),](OTs), (0.3 g, 0.48 mmol) and cod (1.5 mL) in ethanol
(30 mL) was stirred for 4h at room temperature under an inert atmosphere.
This resulted in a color change from red-violet to yellow. The solvent was
removed under vacuum, and the residue was taken up in water (5 mL) and
extracted three times with hexane (5 mL) to remove the excess cod. A yellow oil
remained after the removal of water under vacuum. This was dissolved in
acetone/ethanol (4: l), and cooled to - 10 ', whereby the salt was obtained in
the form of orange-yellow needles. Yield ca. 70-85%.
Received: October 1, 1991
Revised: December 14, 1991 [Z4945IE]
German version: Angew. Chem. 1992, 104, 445
CAS registry numbers:
l-(OTS)z, 139015-58-0; 2-(0T~),, 15694-44-7; 3, 31742-01-5; 4, 139015-59-1;
5a-CIO,, 139015-67-1; 5a-PF6, 139040-89-4; 5b-PF6, 139015-63-7; 5c-PF,,
139015-65-9; 6-(0T~)z,139015-61-5;7, 121922-71-2.
Fig. 3. Crystal structure of 5a-CI0, (SCHAKAL). Distances [A]: Ru-011
2.10(2), Ru-021 2.09(2), Ru-031 2.10(3), Ru-05 2.10(2), Ru-C41 2.17(2), RUC42 2.17(2), Ru-C45 2.17(3), Ru-C46 2.19(4), C41GC42 1.38(1), C45-C46
1.385(9); Angles ["I: 05-Ru-011 81.2(6), 05-Ru-021 162(2), 05-Ru-031
81.3(7), (middle C41 -C42)-Ru-021 95, (middle C45-C46)-Ru-05 95.
ands, two are trans to an olefin double bond (OI), and two
are approximately trans to each other (02) with a 0-Ru-0
angle for the latter of 155". Note that the Ru-01 distances
of 2.158(2) 8, are significantly longer than those of Ru-02
(2.095(2) 8,. Since all of the water-H atoms are hydrogenbonded to the sulfonate groups of the anions, as illustrated
in Figure 2, whereby the crystalline salt forms a chain structure, this difference has to be attributed to a real trans effect
of the double bonds. Thus, in 1, for the first time the influence
of the organic ligand on the metal-water bond is structurally
evident. The effect could not be derived from the structure of
[ (C,H,)RLI(H,O),]~ ,the only other compound comparable
with [Ru(H,O),l2 , because the lack of a threefold crystallographic axis and the different H bonding of the water protons makes the Ru-0 distances unequal.
In Figure 3 the cation of the perchlorate 5a-C10,['71 is
shown. Of the two possible orientations, the tripod ligand
adopts the one that substitutes the 0 1 and 0 1' and 0 2.
Here, the Ru distances to the tripod 0 atom (2.10(2), and
2.09(2) A, respectively) are as long as those to the remaining
aqua ligand, and correspond to the Ru-02 distance in 1(OTs), i.e. the rigid tripod ligand does not reflect the observed trans-effect in the aqua complex. Two oxygen atoms
of the disordered ClO; ion connect the cations via H bonds
to form dimeric units. The Ru-cod distances as well as the
relatively short C = C distances of the coordinated cod double bond, which classify the aqua-Ru complex as a poor back
bonding fragment, are the same in the two complexes within
the limits of error.
The few measurements carried out so far concerning the
kinetics of water exchange in organometallic aqua- and
closely related
all show a rate of exchange
increased by a factor of 103-105 towards the hexaaquametal ions of the same electron configuration. Evidently this
kinetic lability is related to the longer metal-water bond. A
corresponding relationship was noted for the Ru" acetonitrile complexes [Ru(CH3CN),IZ+,[(C6H6)Ru(CH,CN),]z+,
and [(C,H,)Ru(CH,CN),]+, with an increasing exchange
rate of the acetonitrile in this order." 91 The kinetic lability
together with the thermal stability of the dicationic complex
1, and the possibility of a reversible CO addition (Scheme 2),
hopefully mean that diene(aqua) complexes can also act as
effective catalysts.
+
+
442
0 VCH Verlagsgesellschafi mbH,
W-6940 Weinheim. 1992
[I] C. K. Jsrgensen, fnorg. Chem. 1964, 3, 1201-1202.
[2] Y Hung, W.-J. Kung, H. Taube, Inorg. Chem. 1981, 20, 457-463.
[3] a) P. Bernhard, L. Helm, I. Rapaport, A. Ludi, A. E. Merbach, .IChem.
SOC.Chem. Commun. 1984, 302-303; b) M. Stebler-Rothlisberger, W.
Hummel, P.-A. Pittet, H.-B. Biirgi, A. Ludi, A. E. Merbach, Inorg. Chem.
1988,27, 1358-1363.
[4] E. A. Ganja, T. B. Rauchfuss, C. L. Stern, Organometallics, 1991,10,270275.
[5] L. 0. Spreer, 1. Shah, fnorg. Chem. 1981, 20, 4025-4027.
[6] U. Kolle, 9. Fuss, Chem. Eer. 1984, 117, 753-762.
[7] U. Kolle, W. Klaui, Z . Nafurforsch. E 1991, 46, 75-83.
[8] U. Kolle, .IEleetroanal. Chem. Interfacial Electrochem. 1990, 292, 217229; A. Nulton, P. Bailey, P. M. Maitlis, .IChem. SOC.Dalton Trans. 1981,
1997-2002.
[9] Compare D. V. McGrath, R. H. Grubbs, .IAm. Chem. SOC.1991, 113,
3611-361 3.
[lo] W. Weber, P. C. Ford, fnorg. Chem. 1986, 25,1088-1092.
[ l l ] P. Bernhard, H.-9. Biirgi, J. Hauser, H. Lehmann, A. Ludi, Inorg. Chem.
1982. 21, 3936-3941.
[12] M. Stebler-Rothlisberger, A. Salzer, H.-B. Burgi, A. Ludi, OrganomefalI ~ C S1986, 5 , 298-302.
[I 31 Following our observations 2 disproportionated in water on mild warming
(Eo(3 Ru" --+ 2 Ru3+ + Ru) = -0,014 V (calculated from the standard
potentials from Handbook of Chemistry and Physics, 64th Ed., CRC Press,
Boca Raton, FL, USA, 1983, p. D156)
[14] Cf. W. Klaui, Angew. Chem. 1990, 102, 661-670; Angew. Chem. Int. Ed.
Engl. 1990,29,627-637.
[15] G. Laurenczy, L. Helm, A. Ludi, A. E. Merbach, Helv. Chim. Acta 1991,
74, 1236-1238.
[36] Structure data: space group Pmmn (No. 59), a = 6.931(1), b = 24.911(6),
c =7.516(2) A, V =1.9277(8) nm3, 2 = 8/4, p..,, =1.832 g ~ m - crystal
~,
2. =
dimensions 0.4 x 0.3 x 0.2 mm, ENRAF-Nonius CAD4, Mo,,
0.7093 A, 293 K, mi28 scan, 0 < w < 30", extinction coefficients refined to
0.610 x
empirical absorption correction by the $ scan method, 5485
reflections, of which 4381 f > 3a(f), 1724 independent with f > 3u(f),
and 8 < 30" in the structure factor calculation and refinement; nonhydrogen atoms anisotropic, H atoms of the aqua ligands and at C1 isotropic,
remaining H atoms not refined, but included in the structure correction.
107 parameters, R = 0.024, R, = 0.038 (statistically weighted). Further
details from the Fachinformationszentrum Karlsruhe, see [17].
[17] Structure data: space group P2,/c, a =12.515(2), b =12.410(3), c =
23.719(5)A, =101.36", V = 3.612(2) nm3, Z =4, peas = 1.585 g ~ m - ~ ,
crystal dimensions 0.4 x 0.3 x 0.2 mm, ENRAF-Nonius CAD4, Mo,.,
2. = 0.7093 A, 293 K, o scan, 3" 0 < 25", 5989 reflections, extinction
correction, empirical absorption correction by the $ scan method; with
3589 unique reflections with f > 2u(f), 434 parameters, R = 0.046, R. =
0.047 (statistically weighted). Perchlorate disorder about the CI-0 bond,
H bonds CI0,-H,O. Further details of the crystal structure investigation
may be obtained from the Fachinfotmationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH, D-W-7514 Eggenstein-Leopoldshafen 2 (FRG) on quoting the depository number CSD55845, the names of the authors, and the journal citation.
- ~ in
1181 k, for water exchange in [RU(H,O),]~' = 1 . 8 ~ 1 0 - ~ s [Ill;
[(C,H,)Ru(H,0),]2+ =11 sC1 [3b]; k for water exchange in [CpCr(H,O),]*+- 1OM-'s1 [51; k for the reaction [Cp*M(bpy)(H,O)lz+ +
SCN- -[Cp*M(bpy)(SCN)]' =1 . O 5 K 1 s - ', M = Co; 111 M-'s',
M = Rh; 325
M = Ir (J. Schneider, H. Elias, U. Kolle, .ISerb.
Chem. SOC.1990, 55, 695-700).
[19] W. Luginbiihl, P. Zbinden, P. A. Pittet, T. Armbruster, H:B. Biirgi, A. E.
Merbach, A. Ludi, fnorg. Chem. 1991, 30, 2350-2355.
0570-0833/92/0404-0442$3.50+ .25/0
Angew. Chem. Int. Ed. Engl. 31 (1992) No. 4
Документ
Категория
Без категории
Просмотров
4
Размер файла
393 Кб
Теги
preparation, exchanger, cod, structure, complex, reaction, aqua, diener, h2o, ruthenium, ots, ligand
1/--страниц
Пожаловаться на содержимое документа