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Hydroxylamine Hydrazine and Diazene as Unidentate Ligands in Osmium and Ruthenium Complexes.

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Experimental Procedure
1:A solution o f 4 (400 mg.0.3mmol) in dichloromethane (400mL) was vigorously
stirred with CuCl (2.4g, 24 mmol) and N.N,N'.N'-tetramethylethylenediamine
(TMEDA) (3.4mL. 22 mmol) under dry air. The green solution became brown and
viscous, and no unreacted 4 could be detected by TLC after 5 min. After 30 min the
mixture was washed with water (3x 500 mL) and passed through a silica flash
column, eluting with 1 % pyridine/dichloromethane to remove baseline contaminants. The eluate was centrifuged (2.2kG, 2 x 20 min) to remove colloidal copper
salts, then treated with methanol (20mL) to precipitate the polymer. The product
was isolated by centrifugation (2.2kG. 20 min), washed with methanol and diethyl
ether, and dried in vacuo to yield 230 mg (58%) of a leathery lustrous green solid.
m.p. > 300°C; 'HNMR (400MHz, C,D,CI,/C,D,N. 1OOT): S = 0.8-1.5 (76
H), 3.3 (8 H). 4.1-4.5 (28 H). 10.1 (2H): "C NMR (100 MHz. C,D,CI,/C,D,N,
100°C): b =16.6, 22.2,,,,81.2
(v br), 92.8,(v br) 99.5 (v br).,151.1. 172.6:IR (1% C,H,N/
CCI,): t[cm-'] = 2120 (C=C). 1730 (C=O); UVjVIS (1 % C,H,N:CH,CI,): L,,,
[nm] (log E ) = 505 (4.97).873 (5.29):correct C. H, N analysis for C,,H,,,N,O,Zn.
Electroabsorption spectra were recorded and transformed into f 3 ] spectra as described previously 11 ll.
Received: September 30, 1993 [26381TE]
German version: Angew. Chem. 1994,106. 71 1
[l]H. S. Nalwa, Adv. Marer. 1993,5 , 341-357.
[2]Crossley and Burn have reported the preparation of an insoluble porphyrin
polymer, and some soluble conjugated oligomers: M. J. Crossley. P. L. Burn,
J. Chem. Soc. Chem. Commun. 1987,39-40;ibid 1991, 1569-1571.
[3]For reviews of coordination-linked porphyrin and phthalocyanine oligomers
see E. Kellogg, J. G. Gaudiello in Inorganic Material.$ (Eds.: D. W. Bruce, D.
OHare), Wiley, Chichester, 1992, pp 353-396; M. Hanack. S. Deger. A.
Lange, Coord. Chem. Rev. 1988.83,115-136.
[4]The synthesis of 2, 3. and 4 are to be published elsewhere: H. L. Anderson.
Inorg. Chem. 1994,33.982-993.
[5]A. S. Hay, J. Org. Chem. 1960.25.1275-1276.
[6]M. R.Callstrom T. X. Neenan. G. M. Whitesides, Macromolecules 1988,21,
3528-3530; D.R. Rutherford. J. K. Stille. C. M. Elliot, V. R. Reichert, ibid
[7]The intrinsic viscosity was measured at 250°C in 20% pyridine/l.2,4-trichlorobenzene (concentration 1-6 mgmL-') by extrapolating both the viscosity number and the logarithmic viscosity number to infinite dilution.
[8]Preliminary small angle neutron scattering measurements on solutions of 1 in
CHCl,/C,H,N indicate the degree of polymerization is in the range 7- 15. We
thank Dr A. R. Rennie. Cavendish Laboratory. GB-Cambridge. for these
[9]M. Gouterman in The Porphyrins Vol. 3 (Ed.: D. Dolphin), Academic Press,
New York, 1978,pp. 1-166.
[lo]Transition dipole strengths were calculated by integrating extinction coefficient
divided by wavenumber. .$?)/I versus I, using the equation p2 = (9.188x
no)J{e(C)/t}dt,where no is the solvent's refractive index (1.42for CH,CI,) and
pz is the dipole strength in DZ (D = Debye).
[ll]0. M. Gelsen, D. D. C. Bradley, H. Murata. N. Takada, T. Tsutsui, S. Saito,
J. Appl. Phys. 1992,71, 1064-1066.
[I21 S. D.Phillips, R. Worland, G. Yu.T. Hagler, R. Freedman, Y. Cao, V. Yoon,
J. Chiang. W. C. Walker, A. J. Heeger, Ph.v.7. Rev. B Condens. Matter 1989.40,
9751 -9759.
[I31 T. Hasegawa, K. Ishikawa, T. Koda, K. Takeda. H. Kobayashi, K. Kubodera,
Synth. Mer. 1991, 43,3151-3156.
[14] L. Sebastian, G. Weiser. H. BBssler, Chem. Phys. 1981,61, 125-135.
[15] D. J. Lockhart, S. G. Boxer, Proe. Natl. Acad. Sci. USA 1988,85, 107-111.
[I61 We have not yet calculated x'"(- o;O.O,o) for the porphyrin/PMMA films
because the algorithm we use to compute linear optical constants, by iterative
Kramers-Kronig analysis of the transmission data, does not converge well
when the absorption per unit thickness is small.
[17] The x ' ~ 'values reported for most porphyrins are less than lo-" esu; a few give
x ' ~ ' ( - o;w,w,-o) of up to lo-' esu (A. Grund, A. Kaltbeitzet, A. Mathy, R.
Schwarz, C. Bubeck, P. Vermehren, M. Hanack, J. Phys. Chem. 1992, 96,
7450-7454). but for a given material these three-photon resonant
x ' ~ ) ( - o;w,o.-o) values are expected to be much larger than one-photon
resonant f ' ( - w;O,O,w) values (A. Willetts, J. E. Rice, D. M. Burland, D. P.
Shelton, J. Chem. Ph.w 1992,97,7590-7599).
Angew. Chem. I n l . Ed. Engl. 1994,33,No.6
Hydroxylamine, Hydrazine, and Diazene as
Unidentate Ligands in Osmium and Ruthenium
Tan-Yun Cheng, Adrian Ponce, Arnold L. Rheingold,
and Gregory L. Hillhouse*
Diazene NH=NH is one of the most reactive of the nitrogen
hydrides, undergoing disproportionation at - 150 "C in the condensed phase to N, and N,H, .['] Nevertheless, it is a molecule of
fundamental importance, useful as a reagent in stereoselectivecis
hydrogenation of unsaturated organic compounds, and of possible relevance to inorganic and bioinorganic N,-reduction processes."] The stability of diazene is greatly enhanced in solution,
especially in liquid ammonia,[31and by coordination to transition
metals (usually in a bimetallic fashion through both nitrogen lone
pairs) .[41Herein we report the syntheses of new diazene complexes of Ru and Os, including the first structural characterizations of
complexes containing ?'-coordinated H,NNH, and HN=NH
The hydrido complexes 1a and 1 b react with trifluoromethanesulfonic acid (triflic acid) to give H, and the corresponding
trifluoromethanesulfonato complexes 2 a ( i ( C 0 ) = 2071, 2006;
i(OSO,CF,) =1329 cm-') and 2 b ( i ( C 0 ) = 2054, 1985;
C(OSO,CF,) = 1335 cm- '). Hydroxylamine and hydrazine displace the triflate ligands in these complexes to afford the salts 3
l b , M =Os,X = Br
Za,M Ru. X = CI
Zb, M Os,X = Br
3a,M = Ru. X = CI
3b, M = Os, X = Br
48,M = Ru, X = CI
4b,M = Os, XI Br
- Os,
5a. M = Ru, X = CI
Jb, M
X = Br
Prof. G. L. Hillhouse, T.-Y. Cheng, A. Ponce
Searle Chemistry Laboratory, Department of Chemistry
The University of Chicago
5735 S. Ellis Avenue, Chicago, IL 60637 (USA)
Telefax: Int. code + (312)702-0805
Prof. A. L.Rheingold
Department of Chemistry, University of Delaware
Newark, DE 19716 (USA)
[**I This work was supported by the US National Institutes of Health (GM-41650
to G. L.H.) and an undergraduate research fellowship from the Amoco Foundation (to A. P.).
0 VCH Verlagsgesellschaft mbH, 0-69451 Weinheim, 1994
$10.00 + ,2510
Table 1. IR. 'IP and ' H N M R spectroscopic data
and 4, in which hydroxylamine and hydrazine, respectively, coordinate in a unidentate fashion to the
metal center through one of the nitrgen atoms. The
spectroscopic data of the complexes are summa^v(CO)[a]
2069, 2012 2055, 1992 2070, 2010 2058, 1985
2070, 2019
2061, 2001
rized in Table 1. The hydrazine complexes 4 can be
G("P{'H)) [b]
24.86 (s)
-2.24 (s) 27.09 (s)
-2.65 (s)
25.56 (s)
-1.65 (s)
' H N M R : [c]
oxidized with Pb(OAc), at low temperature to give
5.50 (t)
5.46 (t)
4.33 (br. m) 4.35 (br. m)
the stable diazene complexes 5. The complexes 5
(Y = OH,NH,) 'JPH= 4.3 3JpH
= 4.4
exhibit lowfield (6 = 17- 15) ABX, patterns in their
6(M-NH, Y )
8.22 (br.)
8.66 (bi-.) 3.35 (t)
3.56 (t)
'H NMR spectra characteristic of the diazene pro(Y = OH:NH,)
' J H H= 4.5
'J,,,, = 4.9
16.64 id)
16.60 (d)
tons of unidentate trans-HN=NH ligands coupled
'JHH= 29.3 'JHH= 29.4
to two equivalent 31Patoms.[51This synthetic pro6(MNH = N H )
35.43 (dt)
15.53 (dt)
tocol is analogous to that used to prepare the relat3JHH
= 29.3, 'JHH= 29.4,
ed diazene complex P(HN=NH)(CO),(NO)4J., =1.9
4JD,= 2.2
(PPh,),][SO,CF,] which we recently reported.15]
[a] Fluorolube mull. i n cm-'. [b] 202 MHz, CD,CI, solution. 20-C. [c] 500 MHz. CD,CI, solution,
We have not yet been successful in isolating stable
20°C. coupling constants in Hz.
complex cations containing nitrosyl hydride ligands ( M e N H = O ) from the analogous oxidation
of 3a or 3b, although a similar neutral 0 s complex with this
It is noteworthy that while monosubstituted diazenes usually
ligand, [Os(Cl),(CO)(NH=O)(PPh,),l (6), is known.'61
coordinate to metals as cis-NH=NR ligands," complexes of
The molecular structures of 4b and 5 b have been determined
the parent diazene show only trans-HN=NH ligation. With
by X-ray diffraction analyses and are interesting because they
several complexes containing diazene ligands coordinated in a
allow for comparison of hydrazine (4 b) and diazene (5 b) ligands
unidentate fashion now in hand, we are currently exploring the
reaction chemistry of these molecules.
in identical coordination environments.['] Both complex cations
are pseudooctahedral with cis carbonyl and trans phosphane ligands. The 0 s - N (2.181(3) A) and N-N (1.451(7) A) bonds in 4b
are in the normal range for single bonds (Fig. 1 ) ; the 0s-N-N
angle (1 19.3(3)") is somewhat opened from the tetrahedral value.I81
Fig. 2 A perspective view of the complex cation of 5b.
Experimental Procedure
Fig. 1. A perspective view of the complex cation of 4b.
The most significant structural feature of 5b (Fig. 2) is the
unambiguously characterized unidentate trans-HN=NH ligand
coordinated to the 0 s atom. The positions of the H atoms of the
diazene were located and refined.[" The N-N (1.166(17) A)
bond length in 5 b is short, but it is within experimental error of
that expected for a N = N bond. The 0 s - N (2.118(12) A) bond
length is shorter than that in 4b, consistent with the smaller
covalent radius for the sp2-hybridized N atom in diazene compared to the sp3-hybridized N atom in hydrazine. The 0s-N-N
angle (135.9(10)") in 5b is significantly more obtuse than the
idealized 120" trigonal value. A comparison of the metrical
parameters of the diazene ligand of 5 b with those of the isoelectronic HN=O ligand in 6 (in which the nitrosyl hydride ligand
is also unidentate) reveals striking similarities: in 6, N - 0
1.193(7), 0 s - N 1.915(6) A, and g 0 s - N - 0 136.9(6)".[61
'i" VCH
Verlugagesellsc.huft mbH, 0-69451 Wemheim. 1994
All reactions were carried out under argon using dry, air-free solvents.
Zb: To a stirred solution of l b (1.00g, 1.17mmol) [ I l l in CH,CI, (35 mL) was
added HOSO,CF, (0.11 mL). When gas evolution ceased, the solvent volume was
reduced and Et,O was added to precipitate 0.88 g (75% yield) of 2 b as white
crystals. 2 a was prepared analogously in 70% yield from l a .
3b: To a stirred solution of 2 b (0.15 g, 0.15 mmol) in CH,CI, (10 mL) was added
NH,OH (0.025 g%
0.75 mmol) [12]. The solution was stirred for 15 min, additional
NH,OH (0.025 g) was then added. and stirring was continued for 10 min. The
reaction mixture was filtered through Celite, the volume of the filtrate was reduced,
and Et,O was added lo precipitate 0.077 g (50% yield) of 3 b as a white powder. 3 a
was prepared analogously in 90% yield from 2a.
4 b : To a solution of Zb (0.50 g, 0.50mmol) in CH,CI, (30mL) was added 98%
NH,NH, (1.24mL. 0.75 mmol). The solution was stirred for 15 min. additional
NH,NH, (0 5 mL) was then added, and stirring was continued for 15 min. The
solution was filtered, the solvent volume was reduced, and Et,O was added to
precipitate 0.41 g (80 % yield) of 4 b as a white powder. 4 a was prepared analogously
in 90% yield from 2a.
5b: A sample of 4 b (0.10 g, 0.10 rnrnol) was placed in a two-necked 25 mL flask
fitted with a solids-addition sidearmcontainingPb(OAc), (0.05 g, 0.12 minol). The
system was evacuated. CHCI, ( 5 mL) was vacuum transferred at -40°C into the
tlask. and the Pb(OAc), was added portionwise to the cold, stirred solution. After
10 mm, the solvent was removed under vacuum. and the residue was extracted with
CH,CI, (10 mL). The solution was filtered, the solvent volume was reduced. and
petroleum ether was added to precipitate 0.064 g (64% yield) of 5 b as a pale yellow
B iO.00 + .2j/O
Anjiru.. Chem. Inr. Ed. Engl. 1994, 33. No. 6
powder. 5 a was prepared analogously in 4 0 % yield from 4 a , except that the reaction temperature was maintained at - 78 'C.
Received: October 5 , 1993 [Z6394IE]
German version: Angew. Chem. 1994, 106, 703
[l] N. Wiberg. H. Bachhuber, G. Fischer, Angeic Chem. 1972, 84. 889; Angetc.
Chem.In!. Ed. EngI. 1972. 1 1 . 829.
[2] R. A. Back. Rev. Chern. Intermed. 1984. 5 , 293; S. Hunig, H. R. Muller, W.
Thier. Angcw. Chem. 1965, 77. 368; Angew. Chem. I n t . Ed. Engl. 1965, 4. 271;
C. E. Miller, J. Chem. Edirr. 1965. 42. 254; J. M. Manriquez, R . D. Sanner. R.
E. Marsh, J. E. Bercaw. J . Am. Chern. Suc. 1976, 98, 3042; D. Coucouvanis,
A ( ( , . Ch~ri?.Rcs. 1991, 24. 1; R. N. F. Thorneley, R. R. Eady, D. J. Lowe,
,Vami-c (Luiidun) 1978. 272, 5578; R. A. Henderson, G. J. Leigh, C. J. Pickett,
Adv. Inorg. Chem. Rudiuchem. 1983, 27, 198.
[3] C. Willis. R. A. Back. Cun. J Chem. 1973, 51, 3605; R. A. Back. C. Willis, ibid.
1974.52. 2513.
[4] D . Sellmann. A. Brandl, R Endell, Angew. Chrm. 1973, 85, 1122; Angew.
Chmi. Inr. €d. Engl. 1973, f2, 1019: D. Sellmann. K. Jodden, ibrd. 1977.59.480
and 1977, f6.464; D. Sellmann, E. Bohlen, M. Waeber, G. Huttner, L. Zsolnai,
;hid 1985.97,984 and 1985. 24.981 : D. Sellmann, W. Soglowek, F. Knoch, M.
Moll, rhid 1989. f0f.1244 and 1989, 28, 1271: G. Huttner, W. tiartzke, K.
Allinger. ;hid 1974. 86. 860 and 1974, f3, 822; D. Sellmann, J . Organomrr.
Chem. 1972, 44, C46; G. Huttner, W. Gartzke, K. Allinger, h i d . 1975, 91, 47:
D. Sellmann. A. Brandl. R. Endell. ibid. 1973. 49, C22; J. P. Collman, J. E.
Hutchison. M . A. Lopez, R. Guilard, R. A. Reed, J. A m . Chem. Sor. 1991. tf3,
[ 5 ] M R . Smith 1". T.-Y. Cheng, ti. L. Hillhouse. J. A m . Chwn. SUC.1993. fI5.
161 K R. Grundy. C. A. Reed, W. R. Roper, J . Chcm. Soc. Chrm. Commun. 1970,
1501 ; R. D. Wilson, J. A. Ibers. Inurg. Chem. 1979, f8. 336.
[7] Further details of the crystal structure investlgations are available on request
from the Director of the Cambridge Crystallographic Data Centre, 12 Union
Road, GB-Cambridge CB2 1EZ (UK), on quoting the full journal citation.
[ 8 ] Crbslal data for 4b: C,,H,,BrF,N,O,OsP,S,
triclinic, Pi,a =11.434(3), h =
13.?18(4). c=13.859(3)& x=98.17(2), 8=100.31(2). y=104.13(2)". V =
2034.2(9) A 3 . Z = 2.pcJ,cd=1.685 g ~ m - ~ . p ( M o=~ 43.04cm-'.
T = 296K.
Of 12316 ddta collected (Siemens P3, 20,,, = 6 0 ) . 11865 were independent
and 8878 ucre observed (SaF,). All non-hydrogen atoms were anisotropically
refined and phenyl hydrogen atoms were treated as idealized contributions:
those ol' the hydrazine molecule were ignored. The phenyl rings were constrained lo rigid planar hexagons. SHELXTL software was used for all calculations At convergence: R ( F ) = 0.0371, R ( w F ) = 0.0430.
[9] CrystAdatafor5b: C,,H,,BrF,N,O,OsP,S.
monoclinic, P21/c. a = 11.219(2).
h = 14 165(3). r = 25.410(6) A. /I= 93.370(2)", V = 4031.2(15) A', 2 = 4,
= 1.697 gem-', p(MoKr)= 43.44 cm-'. T = 296 K . Of 5774 data collected (Siemens P4,20,,, = 45'). 5272 were independent, and 3701 were observed
( 4 0 E J . All non-hydrogen atoms were anisotropically refined. and hydrogen
atonis were idealized except for the diazene hydrogen atoms which were located
and refined. SHELXTL software was used for all calculations. R ( F ) = 0.0537,
R(n F ) = 0.0624.
1101 M. R. SmithII1.T.-Y. Cheng, ti. L. Hillhouse. Inorg. Chrm. 1992,31,1535, and
references therein.
[ I l l K. R Laing. W. R. Roper, J Chem. Sur. ( A ) 1969, 1889; B. R. James, L. D.
Markham. B. C. Hui, G . L. Rempel, J. Chem. Suc. Dalton Trans. 1973, 2247.
[I21 C . H . Hurd. Inurg. .Qn. 1939, I, 87.
alkenes, dimes, and enones, but they have never been isolated.[21
Neumann et al.["] proposed a germirane or germylene-olefin
complex as a intermediate in the reaction of dimethylgermylene
with styrene, which resulted in the formation of a germacyclopentane. Several other approaches for the preparation of germiranes
have been unsuccessful, for example, reductive elimination of
bromine from di(bromomethy1)germanes by Seyferth et a1.,[2d1
CH insertion of germylcarbenes by M. Jones, Jr. et al.,[2ccl
extrusion of N, from a germapyrazoline from Nefedov, Krebs,
et al.["I and Satge et al.[2g.h1In every case only olefins and
polygermanes were detected. These experimental results were
supported by recent ab initio calculations which indicated that
germiranes are the most likely of the group 14 metallacycles to
undergo cycl~elimination.[~~
Herein we describe the reactions of
the stable germylene 1 [41 with 2,5-dimethyl-2,3,4-hexatriene("tetramethylbutatriene" 2) and N-phenylmaleimide (5) which yield
the first isolable germirane derivatives, bis(alky1idene)germirane 3
and bicyclic germirane 8 (Scheme I), which were characterized
by X-ray crystallography.
Ph 7
Scheme 1. R
Our first approach was the construction of a germirane with
two alkylidene substituents. Tetramethylbutatriene 2 was thought
to be a suitable electron-rich triene for the introduction of exoalkylidene moieties to germirane. Similar reactions have been
successful in the preparation of bis(alkylidene)silirane.[' h1 Thus
when a yellow solution of 1 in benzene was treated with tetramethylbutatriene 2, immediate decolorization was observed and
3 was isolated from the reaction mixture in 3 3 % yield. The
Stable Germirane Derivatives **
Wataru Ando," Harunobu Ohgaki, a n d Yoshio Kabe
1,2-Additions of carbene analogues of the heavier group
14elements with alkenes and alkynes have been used for the synthesis of the corresponding three-membered metallacycles.[llGermirane (germacyclopropane) has been proposed to exist as an
intermediate in reactions of germanediyls ("germylenes") with
Prof. Dr. W Ando, H. Ohgaki, Dr. Y Kabe
Department of Chemistry. University of Tsukuba
Tsukuba. Ibaraki 305 (Japan)
Telefax: Int. code (298)53-6503
This work was supported by a Grant-in-Aid for Scientific Research for Ministry of Education. Science and Culture of Japan. The authors are greatful to
Asai Germanium Institute, Shin-Etsu Co. Ltd., and Tosoh Akzo Corp. for
generous gifts of trichlorogermane, chlorosilanes, and alkyllithium.
Angeit,. Chem. In[. Ed. Engl. 1994. 33, No. 6
Fig. 1. Crystal structure of 3 (ORTEP). Selected bond lengths [A] and angles ["I:
Ge-C(I1 1.95(1). Ge-C(2) 1.96(1), Ge-C(7) 1.95(9), Ge-C(8) 1.99(1). C(l)-C(2)
f.46(2), C(l)-C(5) 1.34(2). C(2)-C(6) 1.33; C(l)-Ge-C(2) 44.0(5), Ge-C(l)-C(Z)
6 8 3 7 1 , Ge-C(2)-C(1) 67.7(7), Ge-C(l)-C(S) 148(1), Ge-C(2)-C(6) 146(1), C(1)C(2)-C(6) 140(1), C(2)-C(l)-C(5) 138(1).
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hydroxylaminen, hydrazine, diazen, osmium, complexes, ruthenium, unidentate, ligand
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