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Bis(-cyclopentadienyl)(1 2 3-triphenyltriphosphanato-P1 P3)-titanium and -zirconium.

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Bis(x-cyclopentadienyl)(1,2,3-triphenyItriphosphanato-P' ,P3)-titanium and -zirconium[']
tion is instantaneous, with a color change from violet to
red or from orange to colorless :
By Kurt Issleib, Grete Wille, and Frieder Krech"]
The treatment of 1,4-dialkali-1,2,3,4-tetraphenyltetraphosphanes with bis(n-cyclopentadieny1)-titanium or -zirconium
dihalides leads, not as in the case of lithium dialkylphosphides['] to compounds of the type [(C,H,),MPR,],, but
(contrary to statements by H . Ko'pf[31)to bis(x-cyclopentadienyl)(l,2,3-triphenyltriphosphanato)-metalcomplexes
( I ) and (2).
The metal :phosphorus ratio can be determined by treatment with iodine, hydrolysis of the oxidation product,
C,H,PI,, and back-titration of the iodine.
Experimental
(1). M ' = Ti
(Z),
M' = Zr
The four-membered metal-phosphorus ring structure of
( I ) and (2) is proved by determination ofmolecular masses
and by 31P-NMR data.
( I ) forms dark violet and (2) orange crystals that are diamagnetic in the solid state and in solution [x, at 295°K
= -0.60and -0.62.10-, cm3 g-' for ( 1 ) and (2),respectively] ;in the solid state they are relatively stable to air, but
in solution are readily oxidized, (2) more easily than ( I ) .
The complexes dissolve as monomers in dioxane (cryoscopic by Beckman's method), are readily soluble in THF,
dioxane, benzene, or toluene but difficultly so in light petroleum or n-hexane, and decompose in water or alcohols.
The mass spectra (70eV) of ( I ) show the molecular ion
(nz/e= 502) and, infer a h , fragments (C,H,),M(PC,H,);,
+>
(PC,H 5); > P(C,H 5); > (PC,H5): > P(C,HS),C (C5H5)'
C 5 H 5 M f ,and C,Hl (rn/e=394, 324, 262, 216, 185, 178,
113, 77), M = Ti.
1
The 31P-NMR spectra of ( I ) and (2) (in THF, 85%
H3P0, as external standard) are ofAX, type, as the Table
shows.
(C,H,),TiCl, or (C,H,),ZrBr, in dioxane is added dropwise during 30min to a hot suspension of an equimolar
amount of Na, P,(C,H,),.6 Dioxane, LizP,(C,H ,),.4 Dioxane, Na,P,(C,H,), .2 Dioxane or K,(PC,H,), ' 2 THF
in dioxane. There is an immediate color change to dark
violet or orange, respectively. The reaction mixture is
boiled under reflux for 30 min, then freed from solvent in a
vacuum. The residue is treated with toluene. After separation of the alkali halide on a G 4 frit, the solution is concentrated to about 10m1, then kept in a refrigerator, whereupon (1) or (2) crystallizes. The crystals are filtered off,
washed twice with ether and dried in a vacuum. M.p.
under argon 243-245°C for ( 1 ) and 233-235°C for (2);
yield 43-60% according to the batch. All manipulation
is done under argon. The amount of solvent is suited to the
ratio and amounts of the components. Example:
Na,P4(C,H,);6Dioxane
12.1 g in 80 ml dioxane,
(C,H,),TiCl, 3 g in 100ml dioxane and 80 ml toluene. In
this case (C,H,P), is isolated from the filtrate after concentration
Received: February 29,1972 [Z 624 IE]
German version: Angew. Chem. 84.582 (1972)
[I] Alkali-Phosphorus Compounds and Their Reactions, Part 66.Part 6 5 : K . Issteib and F . Krech, Z. Anorg. Allg. Chem. 385,47 (1971).
[2] K . Issteib and H . Hackert, 2. Naturforsch. 2/b, 519 (1966).
[ 3 ] H . KQpL Angew. Chem. 83, 914 (1971); Angew. Chem. internat.
Edit. 10, 840 (1971).
Cationic y -0xo-isocyano Complexes of Iron,
Ruthenium, and Osmium(n)[']
By Matthias Schual and Wo2fgang Beck"]
( I ) and (2) were characterized by degradative reactions
in dioxane with ethereal HCl and iodine; the decomposi-
Alkylation of cyano complexes, leading to isocyanide compounds, has long been known[''. In an attempt to prepare
isocyano complexes by treating potassium hexacyanoferrate(1r) with oxonium salts in acetone, we found new,
hexacoordinated, cationic cyano complexes in which a
keto group was in position 3 relative to the isocyanide
group. Analogous ruthenium and osmium complexes are
formed similarly in good yields (ca. 80%). These complexes are apparently formed by acid-catalyzed aldol addition of the acetone, in which it can be assumed that the
carbonium ion of the dimeric acetone is trapped by nucleophilic attack of the coordinated cyano ligand. In fact, the
iron(I1) complex ( I ) is obtained in almost quantitative
yield also from diacetone alcohol or mesityl oxide and
[*] Prof. Dr. K. Issleib, Dr. G. Wille, and Dr. F. Krech
[*] Prof. Dr. W. Beck and DipLChem. M. Schaal
I
, /PR\
,M,
(1)
PA= + 180.9 1
P,= -184.9&1
3230+10
12)
P,= - 181.4+1
P,=- 90.7+1
338.5 F 10
,p,4-
The lower chemical shift 6PBof ( I ) than of (2) is to be
ascribed to a larger electron delocalization P,+Ti'", which
accords with the easier reducibility of (C5H,),TiZf.
Sektion Chemie der Universitat
DDR-402 Halle, Weinbergweg
Angew. Chem. inrernat. Edit. 1 Vol. I 1 (19721 i N o . 6
Institut fur Aiiorganische Chemie der Universitat
8 Mhnchen 2, Meiserstrasse 1 (Germany)
527
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titanium, triphenyltriphosphanato, bis, zirconium, cyclopentadienyl
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