Perfluoroalkyl-substituted triazapentadienes and their metal complexes

Article abstract of DOI:10.1021/ic020550t

Triazapentadienides, C₃F₇-C(=NR)-N=C(NHR)-C₃F₇, result from the reaction of primary amines RNH₂ with the fluorinated imine C₃F₇-CF=N-C₄F₉. The aniline deriv

Full text of DOI:10.1021/ic020550t

Inorg. Chem. 2003, 42, 932−934
Perfluoroalkyl-Substituted Triazapentadienes and Their Metal Complexes
,†
A. R. Siedle,* Robert J. Webb,† Fred E. Behr,‡ Richard A. Newmark,† David A. Weil,†
Kristin Erickson,† Roberta Naujok,† Myles Brostrom,† Mark Mueller,† Shih-Hung Chou,† and
Victor G. Young, Jr.§
3M Corporate Research Laboratories, St. Paul, Minnesota 55144, 3M Specialty Materials
DiVision, St. Paul, Minnesota 55144, and Chemistry Department, UniVersity of Minnesota,
Minneapolis, Minnesota 55455
Received September 11, 2002
Triazapentadienides, C F −C(dNR)−NdC(NHR)−C F , result from
the reaction mixture.5 This acid-catalyzed R-elimination
3
7
3 7
reaction is generally applicable to linear, cyclic, and het-
eroatom-substituted6 perfluoroalkylamines. Addition of 1 to
the reaction of primary amines RNH with the fluorinated imine
2
C F −CFdN−C F . The aniline derivative (R ) Ph) is a weak
3
7
4 9
monoprotic acid in dmso. Its conjugate base exhibits an extensive
coordination chemistry. It acts as a bidentate ligand toward the
molecular fragments Pd(C H ), Rh(c-C H ), Ir(c-C H ), and Rh-
(2) (a) Kim, J.; Hwang, J. W.; Kim, Y.; Lee, M. H.; Han, Y.; Do, Y. J.
Organomet. Chem. 2001, 620, 1. (b) Qian, B.; Ward, D. L.; Smith,
M. R., III. Organometallics 1998, 17, 3070. (c) Rahim, M.; Taylor,
N. J.; Xin, S.; Collins, S. Organometallics 1998, 17, 1315. (d) Cheng,
M.; Lobkovsky, E. B.; Coates, J. J. Am. Chem. Soc. 1998, 120, 11018.
(e) Radzewich, C. E.; Coles, M. P.; Jordan, R. F. J. Am. Chem. Soc.
1998, 120, 9384. (f) Ihara, E.; Young, V. G., Jr.; Jordan, R. F. J. Am.
Chem. Soc. 1998, 120, 8277. (g) O’Keefe, B. J.; Hillmyer, M.; Tolman,
W. B. J. Chem. Soc., Dalton Trans. 2001, 2215. (h) Jazdzewski, B.
A.; Holland, P. L.; Pink, M.; Young, V. G., Jr.; Spencer, D. J. E.;
Tolman, W. B. Inorg. Chem. 2001, 40, 6097. (i) Panda, A.; Stender,
M.; Wright, R. J.; Olmstead, M.; Klavins, P.; Power, P. P. Inorg. Chem.
2002, 41, 3909.
(3) Other exemplary uninegative diaza ligands include phosphori-
namines: (a) Cavell, R. G.; Babu, R. P. K.; Kasani, A.; McDonald,
A. J. Am. Chem. Soc. 1999, 121, 5805. (b) Kasani, A.; McDonald,
R.; Cavell, R. G. Organometallics 1999, 18, 3775. Arylguanidates:
(c) Holman, K. T.; Robinson, S. D. Sahajpal, A.; Stead, J. W. J. Chem.
Soc., Dalton Trans. 1999, 15. (d) Maia, J. R.; Gazard, P. A.; Kilner,
M.; Batsamov, A. S.; Howard, J. A. K. J. Chem. Soc., Dalton Trans.
1997, 4625. Aminidates (e) Barker, J.; Kilner, M., Coord. Chem. ReV.
1994, 133, 219. (f) Edelman, F. T. Top. Curr. Chem. 1996, 179, 113.
(g) Jayaratne, K. C.; Keaton, R. J.; Henningsen, D. A.; Sita, L. R. J.
Am. Chem. Soc. 2000, 122, 10490. (h) Chen, C.-T.; Rees, L. H.;
Cowley, A. R.; Green, M. L. H. J. Chem. Soc., Dalton Trans. 2001,
1761. (i) Gomez, R.; Green, M. L. H. J. Chem. Soc., Dalton Trans.
1996, 939. (j) Barbier-Baudry, D.; Bouazza, A.; Brachais, C. H.;
Dormond, A.; Visseaux, M. Macromol. Rapid Commun. 2000, 21,
213. (k) Keaton, R. J.; Jayaratne, K. C.; Henningsen; Koterwas, L.
A.; Sita, L. R. J. Am. Chem. Soc. 2001, 123, 6197. Aminotropon-
imines: (l) Brasen, W. R.; Holmquist, H. E.; Benson, R. E. J. Am.
Chem. Soc. 1961, 83, 3125. (m) Roesky, P. W. Chem. Soc. ReV. 2000,
29, 335. 5-Aza-semicorrins: (n) Leutenegger, U.; Umbricht, G.; Fahrni,
C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143. Two excellent
comprehensive reviews have recently appeared. One (Bourget-Merle,
L.; Lappert, M. F.; Severn, J. R. Chem. ReV. 2002, 102, 3031) discusses
â-diketoiminato metal complexes. The other (Piers, W.; Emslie, D. J.
H. Coord. Chem. ReV. 2002, 233-234, 131) treats, inter alia, NN,
NNN, NO, NCN, and NON donor ligands.
3
5
8
12
8 12
(CO)2. The chelates [C F −C(NPh)−N−C(NPh)−C F ] M, M ) Mg,
3
7
3 7 2
Mn, Fe, Co, Ni, Cu, Zn, and Pd, were prepared. In the
crystallographically characterized Co complex, the metal is 3d7, S
3
) /2 and tetrahedrally coordinated. Spin densities at carbon in
the C H and C F groups were estimated from the 1H and 19F
6
5
3 7
contact shifts. Spin delocalization onto phenyl sp2 carbons is ∼10
times greater than onto the fluorinated sp3 carbons.
Organic ligands form the cornerstone of a broad field of
inorganic chemistry, that of coordination compounds. For
example, O,O-â-diketone complexes, [R-C(O)-CH-C(O)-
R]M, are one of the largest classes of transition metal and
main group chelates; examples containing a substantial
fraction of the elements in the periodic table are known.1
Diaza analogues, in which the ligating oxygen atoms are
replaced by isoelectronic NR groups, â-ketimine complexes,
[R-C(NR)-CH-C(NR)-R]M, show chemical similarities
and have recently been investigated as polymerization
catalysts as well as models for copper metalloproteins2,3 We
present a survey of a broad, new class of ligands, perfluoro-
alkyl-substituted triazapentadienes of the type RfC(dNR)-
NdC(HNR)Rf (Rf ) perfluoroalkyl). They exhibit substantial
scope and diversity in their chemistry that we believe may
rival that of diketones and diketimines.4
(4) Trifluoroacetamidine, HNdC(CF3)-NH2, undergoes a condensation
reaction in the presence of platinum hydrides to liberate NH3 and form
compounds containing the HN-C(CF3)-N-C(CF3)-NH ligand
among which the RuH(CO)(PPh3)2 complex was characterized crys-
tallographically. Hursthouse, M. B.; Mazid, M. A.; Robinson, S. D.;
Sahajpal, A. J. Chem. Soc., Dalton Trans. 1994, 3615. We thank a
reviewer for drawing notice to these ingenious syntheses.
(5) Petrov, V. A.; Belen’lii, G. G.; German, L. S. IzV. Akad. Nauk SSSR,
Ser. Khim. 1985, 1934. Aluminum chlorofluoride has also been used
as a catalyst: Petrov, V. A.; Krespan, C. G.; Smart, B. E. J. Fluorine
Chem. 1996, 77, 139.
When (C4F9)3N and SbF5 are heated to ∼140 °C, loss of
C4F10 occurs and the imine C3F7-CFdNC4F9, 1, distills from
* Author to whom correspondence should be addressed. E-mail:
arsiedle@mmm.com.
† 3M Corporate Research Laboratories.
‡ 3M Specialty Materials Division.
§ University of Minnesota.
(1) Siedle, A. R. In ComprehensiVe Coordination Chemistry; Wilkinson,
G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon: New York,
1987; Vol. 2, p 365.
(6) Banks, R. E.; Burling, E. D. J. Chem. Soc. 1965, 6077.
932 Inorganic Chemistry, Vol. 42, No. 4, 2003
10.1021/ic020550t CCC: $25.00 © 2003 American Chemical Society
Published on Web 01/21/2003

COMMUNICATION
aniline in diethyl ether at 25 °C results in a series of
addition-HF elimination steps, and C3F7-C(dNPh)-
NdC(PhNH)-C3F7, 2 (65% yield), and insoluble PhNH2‚
3HF are produced. Pale yellow 2 may be readily purified
by evaporation of the solvent and recrystallization from
heptane or vacuum sublimation.7,8 This quite general syn-
thesis of triazapentadienes succeeds with a wide variety of
primary amines of diverse functionality so long as they do
not contain other acidic groups (NH2, CO2H, OH, SH).9
Chiral amines can be employed as well. Anilines containing
electron-releasing groups such as p-OMe undergo instead
intramolecular cyclization to give benzopyrimidines. Mono-
substituted hydrazines, RN2H3, yield the corresponding 1-R-
3,5-(C3F7)2-1,2,4-triazoles.
Figure 1. ORTEP drawing of [C3F7-C(NPh)-N-C(NPh)-C3F7]2Co, 17.
Perfluoroalkyltriazapentadienes are weak monoprotic ac-
ids: 2 and C3F7-C(dNR)-NdC(NRH)-C3F7 (R ) C6H4-
NdN-C6H5), 3, have pKa’s of 14.3 and 13.8, respectively,
in dimethyl sulfoxide, cf. 13.3 for (MeCO)2CH2.10 Salts of
[C3F7-C(NPh)-N-C(NPh)-C3F7]- may be obtained using
a wide variety of onium hydroxides in methanol. Treatment
of 2 with n-BuLi in ether or THF affords Li[C3F7-C(NPh)-
N-C(NPh)-C3F7], 4. This reacts with MeI, Me3SiCl, Ph3-
PAuCl, and MeHgCl and to give C3F7-C(dNPh)-
NdC(NPhR)-C3F7, R ) CH3 (5), SiMe3 (6), AuPPh3 (7),
and HgMe (8), respectively. 5-7 contain C3F7 groups that
are inequivalent by 19F NMR, which indicates that the
conjugate base of 2 acts as a monodentate ligand in these
compounds. In solution, 8 comprises a mixture of two
isomeric η1 compounds in which the MeHg moiety is
attached to either the central or terminal nitrogen positions.
These interconvert slowly on the NMR time scale, but only
the former isomer is observed in crystals.
Most useful for the synthesis of transition metal derivatives
are Ag[C3F7-C(NPh)-N-C(NPh)-C3F7], 9, K[C3F7-
C(NPh)-N-C(NPh)-C3F7)], 10, and Mg[C3F7-C(NPh)-
N-C(NPh)-C3F7]2, 11, prepared from 2 and Ag2O in
refluxing CH3CN, KH in THF, and (C5H5)2Mg in toluene at
25 °C, respectively.
Reaction of 9 with [(C3H5)PdCl]2, [Rh(CO)2Cl]2, and
(COD)MCl2 (M ) Rh, Ir) in CH3CN at room temperature
affords [C3F7-C(NPh)-N-C(NPh)-C3F7]E, E ) Pd(C3H5),
12, Rh(CO)2, 13, Rh(COD), 14, and Ir(COD), 15, respec-
tively (COD ) c-C8H12). Treatment of 10 with FeI2, CoI2,
CuCl2, and Pd(CF3CO-CH-COCF3)2 in THF produces the
symmetrical bis(chelates) [C3F7-C(NPh)-N-C(NPh)-
C3F7]2M where M ) Fe (16), Co (17), Cu (18), and Pd (19).
The nickel complex, M) Ni (20), was obtained from 11 and
NiBr2(dimethoxyethane) in toluene at 70 °C.
Advantage can be taken of the acidic proton in 2 to prepare
additional members of the symmetrical chelate set through
reactions with compounds having polar metal-carbon bonds.
The compounds [C3F7-C(NPh)-N-C(NPh)-C3F7]2M, M )
Mn (21) and Zn (22), were obtained upon treatment with
(C5H5)2Mn and Me2Zn, respectively. With the exception of
6, 7, and 11 (water reactive) and 21 (O2 reactive), the new
compounds reported here are air-stable. They have the useful
property of being soluble in both hydrocarbon (C6H14) and
fluorous (C6F14) solvents.
An ORTEP view of [C3F7-C(NPh)-N-C(NPh)-C3F7]2-
Co (17) is shown in Figure 1.11 In it, cobalt is tetrahedrally
coordinated, with the angle between the two CoN2 planes
being 92°; d(Co-N)av is 1.968(2) Å. This geometry helps
to minimize nonbonded repulsion among the C6H5 rings. The
CoN3C2 ring is asymmetric: d(C-N)av to N(1,3,4,6) is
1.307(4) Å but d(C-N)av to N(2,5) is much longer,
1.338(4) Å. The bite distance of the ligand is 2.870 Å.
(7) A closely related compound, the C7F15 analogue of 2, was observed
by GC/MS (but not isolated) among the five products of the reaction
of C7F15CN with aniline: Paciorek, K. J. L.; Nakahara, J. H.; Kratzer,
R. H. J. Fluorine Chem. 1985, 30, 241.
(8) 2: Mp 87.8 °C, ∆Hfus 31.3 kJ mol-1. Molar conductance: 15.8 ohm-1
cm2 mol-1 (2.2 × 10-3 M in MeNO2). HRMS: m/z 559.0728 (M+,
calcd 559.0724), 390.0834 (M+ - C3F7). IR (Nujol) (Raman, neat):
3200, 1682 (1691) 1633 (1625), 1593 (1590) cm-1. UV (isooctane):
λ
max 207 (log ꢀ 4.34), 266 (3.87) nm. 15N NMR (60.8 MHz, 1,2-C2D2-
Cl4, 300 K, with respect to external NH3, indirectly observed via a 1H
GHMBC pulse sequence): δ 288.4 (s, N1), 226.3 (s, N3), 113.7 (d,
JNH 93 Hz, N5). Assignments were confirmed by 15N labeling at
terminal Nl,5 through synthesis of 2 from Ph15NH2. 19F NMR (376.2
MHz, dmso, 300 K): the spectra disclose two inequivalent C3F7 groups
in which the two different R-CF2 groups show geminal inequivalence;
but only one of the two inequivalent â-CF2 groups shows geminal
inequivalence [δ -126.39 (2F, â-CF2), -125.69 and -125.28 (2F,
â-CF2, AB multiplet, JAB 291 Hz), -118.76 and -114.46 (2F, R-CF2,
AB multiplet, JAB 268 Hz), -116.13 and -114.50 (2F, R-CF2, AB
multiplet, JAB 270 Hz), -80.14 and -79.90 (6F, CF3)]. The 19F
resonances are broad (w/2 ∼10-20 Hz). NMR spectra are field,
temperature, and solvent dependent on account of both a 1-5
prototropic shift and at least one additional, low-temperature process.
Dynamics in 2 have been explored by crystallographic, DNMR, and
computational methods. The results will be reported elsewhere.
(9) This is not a severe limitation because such groups can often be masked
or protected. For example, (p-NO2Ph)2N3C2(C3F7)2H, prepared from
1 and p-nitroaniline, can be reduced (H2, Pd/C) to (p-NH2Ph)2N3C2-
(C3F7)2H, which is unobtainable directly from p-phenylenediamine.
Subsequent diazotization with [NO][BF4] in CH3CN yields [(p-N2-
Ph)2N3C2(C3F7)2H](BF4)2, coupling of which with 2-naphthol (Py,
CH3CN) affords [4-(2-HO-C10H8NdN)Ph]2N3C2(C3F7)2H. Coupling
with p-Me2NC6H4CHdCH-CHO and elimination of water yields the
Schiff base (p-Me2NC6H4CHdCH-CHdN-C6H4)2N3C2(C3F7)2H.
(10) By potentiometric titration with methanolic [Bu4N]OH; cf.: Bordwell,
F. G. Acc. Chem. Res. 1988, 21, 456.
(11) Crystal data: red-orange plates from C6H14, P1h (triclinic), a )
11.706(2) Å, b ) 12.112(2) Å, c ) 17.756(4) Å, R ) 102.939(3)°, â
) 102.498(4)°, γ ) 106.230(3)° at 173 K with Mo KR radiation, V
) 2248.7(3) Å3, Z ) 2, FW ) 1175.55, d(calcd) ) 1.736 g cm-3
,
abs coeff ) 0.537 mm-1, max/min transmission ) 1.000/0.908. Final
R [I > 2σ(I)]: R1 ) 0.04399, wR2 ) 0.1083. R indices (all data):
R1 ) 0.0657, wR2 ) 0.1233. X-ray crystallographic files (CIF) are
available as Supporting Information.
Inorganic Chemistry, Vol. 42, No. 4, 2003 933

COMMUNICATION
Cobalt in 17 is high spin 3d7, S ) /2 (µeff ) 4.05 µB in
CD2Cl2 at 300 K by NMR methods). Even so, well-resolved
1H, 13C, and 19F NMR spectra were obtained and assigned
with the aid of 1H-13C 2D HMQC spectroscopy.12 Chemical
shifts in 17 relative to the diamagnetic Zn complex 2213
comprise contact shifts,14 and, following Eaton et al.,15 they
were used to calculate spin densities at the o-, m-, and
p-carbon positions in the ligand phenyl rings: 13.3, -2.0,
and 9.6 e × 10-3 respectively. Spin densities in the C3F7
moieties are much lower: -17, -6, and 8 e × 10-4 for the
R- and â-CF2 and CF3 carbon nuclei, respectively. Spin
delocalization through π bonds in the C6H5 rings is thus much
more effective than through σ bonds in the C3F7 groups
3
despite the strong electron-withdrawing effect of fluorine.
Supporting Information Available: Crystallographic data in
CIF format and experimental details for the collection of crystal-
lographic data. Experimental details for the synthesis of 1, 2, and
17. This information is available free of charge via the Internet at
http://pubs.acs.org.
IC020550T
(13) 22: 1H NMR (599.7 MHz, CD2Cl2, 300 K) δ 7.29 (m, 8H, Hmeta),
7.25 (m, 4H, Hpara), 6.64 (m, 8H, Hortho); 13C (150.8 MHz) δ 158.9 (t,
2JCF 23 Hz, NCN), 142.9 (4C, Cipso), 129.7 (8C, Cmeta), 126.9 (4C,
JCF 272 Hz, CF3CF2); 19F (564.2 MHz) δ -80.5 (CF3), -104.5
(CF2N), -123.4 (CF3CF2). The 1H spectrum shows more than the
expected number of lines. We believe that the pairwise degeneracy
of Ho and Hm is lifted due to restricted rotation of the phenyl rings.
Assignments were confirmed by a 2D 1H-13C experiment. Mp: 130-
131 °C. HRMS: m/z 1180.0749 (M+). IR: 1558 cm-1. UV (isooctane)
(12) 17: 1H NMR (599.7 MHz, CD2Cl2, 300 K): δ 15.3 (s, 8H, w/2 46
Hz, Hmeta), -32.2 (s, 4H, w/2 57 Hz, Hpara), -48.0 (s, 8H, w/2 720
Hz, Hortho). 13C (150.8 MHz): δ 534.3 (s, 8C, w/2 155 Hz, Cortho),
320.2 (s, 4C, w/2 219 Hz, Cpara), 155.1 (q, 4C, JCF 289 Hz, w/2 108
Hz, CF3), 135.6 (t, 4C, JCF 256 Hz, w/2 186 Hz, CF3CF2), 106.6 (br
s, 4C, w/2 334 Hz, CF3CF2CF2), 42.9 (br s, 2C, w/2 204 Hz, Cring ipso),
-24.8 (br s, 8C, w/2 59 Hz, Cmeta). 19F (564.2 MHz): δ -74.2 (s,
12F, w/2 39 Hz, CF3), -117.61 (s, 8F, w/2 106 Hz, CF3CF2), -127.8
(s, 8F, w/2 205 Hz, NCF2). Chemical shifts are in ppm relative to
internal (CH3)4Si (1H and 13C) and CCl3F (19F). Mp: 130.5-131 °C.
HRMS: m/z 1175.0612 (M+), 1006.1220 (M+ - C3F7). UV (iso-
octane): λmax 321 nm (log ꢀ 4.29). IR: 1546, 1480 cm-1. Raman:
1530, 1464 cm-1. Anal.: Calcd (found) for C40H20CoF28N6: C, 40.8
(41.0); H, 1.7 (1.7); Co, 5.0 (4.9); N, 7.1 (7.1). Crystals suitable for
X-ray diffraction studies were grown by slow evaporation of a heptane
solution.
λmax (log ꢀ): 253 (3.74), 337 (4.32). IR: 1580, 1507, 1489 cm-1
.
Raman: 1647, 1581, 1560 cm-1. Anal.: Calcd (found) for C40H20F28N6-
Zn: C, 40.6 (40.8); H, 1.7 (1.6); N, 7.1 (7.0); Zn, 5.5 (5.5).
(14) 1H NMR for the p-tolyl analogue of 18: δ 33.8 (CH3), 15.0 (Hmeta),
-47.4 (Hortho). That the p-CH3 and Hpara 1H shifts are of opposite sign
indicates that the paramagnetic shifts are primarily contact in origin.
(15) (a) Eaton, D. R.; Josey, A. D.; Benson, R. E.; Phillips, W, D.; Cairns,
T. L. J. Am. Chem. Soc. 1962, 84, 4100. (b) Eaton, D. R.; Josey, A.
D.; Phillips, W. D.; Benson, R. E. J. Chem. Phys. 1962, 37, 347. (c)
Eaton, D. R.; Josey, A. D.; Phillips, W. D.; Benson, R. E. Mol. Phys.
1962, 5, 407. (d) Eaton, D. R.; Josey, A. D.; Benson, R. E. J. Am.
Chem. Soc. 1967, 89, 4040.
934 Inorganic Chemistry, Vol. 42, No. 4, 2003