Tuning of the electronic and optical properties of manganese(I) sesquifulvalene complexes

Article abstract of DOI:10.1021/om960571t

Template syntheses of sesquifulvalenes (2,4,6-cycloheptatrien-1-ylidene)cyclopentadiene (1) and [(2,4,6-cycloheptatrien-1-ylidene)ethenylidene]cyclopentadiene (2) lead to air-stable complexes [(1)Mn(CO)₂L]BF₄ (4) and [(2)Mn(CO)₂L]BF₄ (8) (a, L = CO; b, L = P(OMe)₃; c, L = PPh₃) The different σ-donor/π-acceptor abilities of the ligands L allow a tuning of the electronic and optical properties of complexes 4 and 8, which are particularly studied by UV/vis spectroscopy. The first molecular hyperpolarizabilities β of complexes 4 and 8 have been determined in dichloromethane and acetonitrile solutions by hyper Raleigh scattering. The X-ray crystal structures of 4b, 8b, and of the alkenylcyclopentadienyl complex [4,5η-(2,4,6-cycloheptatrien-1-yl)-η ⁵-cyclopentadienyl]dicarbonylmanganese(I) (5) are reported.

Full text of DOI:10.1021/om960571t

4984
Organometallics 1996, 15, 4984-4990
Tu n in g of th e Electr on ic a n d Op tica l P r op er ties of
Ma n ga n ese(I) Sesqu ifu lva len e Com p lexes
Matthias Tamm* and Alexander Grzegorzewski
Institut fu¨r Anorganische und Analytische Chemie, Freie Universita¨t Berlin,
Fabeckstrasse 34-36, D-14195 Berlin, Germany
Thomas Steiner
Institut fu¨r Kristallographie, Freie Universita¨t Berlin,
Takustrasse 6, D-14195 Berlin, Germany
Thomas J entzsch and Wolfgang Werncke
Max-Born-Institut fu¨r Nichtlineare Optik und Kurzzeitspektroskopie,
Rudower Chaussee 6, D-12489 Berlin, Germany
Received J uly 10, 1996X
Template syntheses of sesquifulvalenes (2,4,6-cycloheptatrien-1-ylidene)cyclopentadiene
(1) and [(2,4,6-cycloheptatrien-1-ylidene)ethenylidene]cyclopentadiene (2) lead to air-stable
complexes [(1)Mn(CO)2L]BF4 (4) and [(2)Mn(CO)2L]BF4 (8) (a , L ) CO; b, L ) P(OMe)3; c,
L ) PPh3). The different σ-donor/π-acceptor abilities of the ligands L allow a tuning of the
electronic and optical properties of complexes 4 and 8, which are particularly studied by
UV/vis spectroscopy. The first molecular hyperpolarizabilities â of complexes 4 and 8 have
been determined in dichloromethane and acetonitrile solutions by hyper Raleigh scattering.
The X-ray crystal structures of 4b, 8b, and of the alkenylcyclopentadienyl complex [4,5η-
(2,4,6-cycloheptatrien-1-yl)-η5-cyclopentadienyl]dicarbonylmanganese(I) (5) are reported.
In tr od u ction
In recent years, the development and synthesis of new
materials with large optical nonlinearities have become
an important area of research.1 With a few exceptions2
the majority of organic compounds exhibiting large SHG
(second harmonic generation) efficiencies are polarizable
dipolar molecules with a π-conjugated electron-donor-
acceptor arrangement. These requirements are fulfilled
by sesquifulvalene (1), and substantial first molecular
hyperpolarizabilities â have been predicted for ses-
quifulvalene derivatives based on theoretical calcula-
tions.3 As the instability4 of 1 does prevent applications
in optical device technology, no experimental studies of
the nonlinear optical properties of 1 or related organic
derivatives thereof had been undertaken. In contrast,
complexation of 1 by transition metal fragments leads
to stable organometallic compounds,5-7 which are cur-
rently receiving considerable attention in the field of
F igu r e 1. Canonical presentations for sesquifulvalene
derivatives.
nonlinear optics.8 We had therefore initiated a program
to synthesize stable organometallic complexes of the
sesquifulvalene derivatives (1) and (2) (Figure 1) as
potential candidates for nonlinear optical applications
and reported on the template syntheses of 1 and 2 at
the Mn(CO)3 metal fragment giving complexes 4a and
8a .7 Independently of our approach, Heck et al. have
recently published heterobimetallic iron/chromium ses-
quifulvalene derivatives. These complexes exhibit first
molecular hyperpolarizabilities that are among the
highest values ever measured for organometallic com-
plexes.6
X Abstract published in Advance ACS Abstracts, October 15, 1996.
(1) (a) Williams, D. J . Angew. Chem. 1984, 96, 637; Angew. Chem.,
Int. Ed. Engl. 1984, 23, 690. (b) Chemla, D. S.; Zyss, J . Nonlinear
Optical Properties of Organic Molecules and Crystals; Academic
Press: Orlando, Fl, 1987. (c) Burland, D. M. Chem. Rev. 1994, 94, 1.
(d) Marks, T. J .; Ratner, M. A. Angew. Chem. 1995, 107, 167; Angew.
Chem., Int. Ed. Engl. 1995, 34, 155.
(2) (a) Lambert, C.; Stadler, S.; Bourhill, G.; Bra¨uchle, C. Angew.
Chem. 1996, 108, 710; Angew. Chem., Int. Ed. Engl. 1996, 35, 644. (b)
Bahl, A.; Grahn, W.; Stadler, S.; Feiner, F.; Bourhill, G.; Bra¨uchle, C.;
Reisner A.; J ones, P. G. Angew. Chem. 1995, 107, 1587; Angew. Chem.,
Int. Ed. Engl. 1995, 34, 1485. (c) Dhenaut, C.; Ledoux, I.; Samuel, I.
D. W.; Zyss, J .; Bourgault, M.; Le Bozec, H. Nature 1995, 374, 339. (d)
Ashwell, G. J .; J efferies, G.; Hamilton, D. G.; Lynch, D. E.; Roberts,
M. P. S.; Bahra, G. S.; Brown C. R. Nature 1995, 375, 385.
(3) Morley, J . O. J . Am. Chem. Soc. 1988, 110, 7660.
The two-level model is a simple tool to describe the â
response of a π-conjugated donor/acceptor molecule in
terms of its electronic and spectroscopic properties.9
(5) (a) Cais, M.; Eisenstadt, A. J . Am. Chem. Soc. 1967, 89, 5468.
(b) Brownstein, S. K.; Gabe, E. J .; Hynes, R. C. Can. J . Chem. 1992,
70, 1011.
(6) Behrens, U.; Brussard, H.; Hagenau, U.; Heck, J .; Hendrickx,
E.; Ko¨rnich, J .; van der Linden, J . G. M.; Persoons, A.; Spek, A. L.;
Veldman, N.; Voss, B.; Wong, H. Chem. Eur. J . 1996, 2, 98.
(7) Tamm, M.; Grzegorzewski, A.; Bru¨dgam, I. J . Organomet. Chem.
1996, 519, 217.
(8) Long, N. J . Angew. Chem. 1995, 107, 37; Angew. Chem., Int. Ed.
Engl. 1995, 34, 6.
(4) (a) Bingmann, H.; Beck, A.; Fritz, H.; Prinzbach, H. Chem. Ber.
1981, 114, 1679. (b) Schenk, W. K.; Kyburz, R.; Neuenschwander, M.
Helv. Chim. Acta 1975, 58, 1099.
(9) (a) Oudar, J . L.; Chemla, D. S. J . Chem. Phys. 1977, 66, 2664.
(b) Hendrickx, E.; Clays, K.; Persoons, A.; Dehu, C.; Bredas, J . L. J .
Am. Chem. Soc. 1995, 117, 3547.
S0276-7333(96)00571-7 CCC: $12.00 © 1996 American Chemical Society

Manganese(I) Sesquifulvalene Complexes
Organometallics, Vol. 15, No. 23, 1996 4985
F igu r e 2.
Equation 1 (Figure 2) shows that the static first molec-
ular hyperpolarizability âo depends on the dipole mo-
ment difference ∆µeg, the electronic transition moment
Meg and the energy of transition hωeg, respectively,
between the ground state g and excited state e of an
intramolecular charge transfer excitation. This correla-
tion expressed by eq 1 clearly shows one major obstacle
to designing effective push-pull NLO chromophores
(“nonlinearity-transparency trade-off”):10 on the one
hand, it is desirable to lower the energy of the CT
transition in order to increase âo, which does result in
compounds with long-wave absortions;11 on the other
hand, the use of a second-order NLO material for laser
frequency doubling (second harmonic generation) re-
quires the compound to be transparent for the laser
wavelength λ as well as for λ/2.2a,b,10 For instance, in
the technically significant doubling of diode laser fre-
quencies12 absorptions around 800 nm (λ) and 400 nm
(λ/2) should be avoided. Furthermore, the method of
choice for the determination of â of an ionic compound
in solution is the recently developped hyper Raleigh
scattering technique.13 Usually, this experiment is
performed with a Nd:YAG laser (λ ) 1064 nm) and the
frequency-doubled scattered light (λ/2 ) 532 nm) is
measured. We had therefore assumed that it might be
difficult to measure the intensity of the scattered light
in the case of the manganese(I) sesquifulvalene com-
plexes 4a and 8a , which are red to purple in color and
exhibit strong absorptions around 500 nm in their UV/
vis spectra.7
F igu r e 3. ORTEP drawing of 5: projection on the cyclo-
pentadienyl plane. Note that the molecule is placed on
a crystallographic mirror plane bisecting through C1, C4,
and Mn.
Sch em e 1
However, these complexes offer the possibility of
tuning their electronic and spectroscopic properties by
carbonyl substitution reactions allowing, in principle,
the adaptation of this system to a given laser, and in
this contribution we wish to report on the syntheses of
phosphite (4b, 8b) and phosphine complexes (4c, 8c)
derived from 4a and 8a along with the first molecular
hyperpolarizabilities of complexes 4 and 8.
at 1968 and 1913 cm-1, which can be assigned to the
symmetric (A1) and asymmetric (B1) stretching modes
expected for the alkenylcyclopentadienyl complex 5.
Resu lts a n d Discu ssion
Syn th esis a n d Ch a r a cter iza tion of 5. A widely
used method for the preparation of CpMn(CO)2L com-
plexes from CpMn(CO)3 is the photochemical introduc-
tion of a labile alkene ligand, e.g. cis-cyclooctene, which
is then easily substituted by other ligands such as
isocyanides or phosphines.14 A similar route is em-
ployed by irridation of complex (C7H7-η5-C5H4)Mn(CO)3
(3a ), which contains an uncoordinated cycloheptatrienyl
unit and does therefore have the possibility of chelate
formation (Scheme 1). If the reaction (in cyclohexane)
is followed by IR spectroscopy, the CO absorptions of
the starting material 3a at 2024 (A1) and 1942 cm-1 (E)
disappear, whereas two new absorptions are observed
1
After sublimation 5 is obtained in 61% yield. The H
and 13C NMR spectra indicate that the 2,4,6-cyclohep-
tatrien-1-yl unit is η2-coordinated via the 4,5-carbon
atoms as these resonances are significantly shifted to
higher field upon binding to the metal center. This
assumption is confirmed by the X-ray structure analysis
(Figure 3).
All metal-carbon bond lengths and angles (Table 1)
fall in the range observed for other complexes of the type
CpMn(CO)2(η2-alkene).15 The cycloheptatrienyl unit in
5 adopts a boat conformation and is coordinated without
any strain when compared to the structures of cyclo-
heptatriene16 or substituted cycloheptatriene rings.17
This perfect fit results in an extraordinary stability of
(10) Ledoux, I.; Zyss, J .; J utand, A.; Amatore, C. Chem. Phys. 1991,
150, 117.
(11) Marder, S. R.; Beratan, D. N.; Cheng, L.-T. Science 1991, 252,
103
(12) Staring, E. G. J . Recl. Trav. Chim. Pays-Bas 1991, 110, 492.
(13) (a) Clays, K.; Persoons, A. Phys. Rev. Lett. 1991, 66, 2980. (b)
Clays, K.; Persoons, A. Rev. Sci. Instrum. 1992, 63, 3285.
(14) Lentz, D.; Kroll, J .; Langner, C. Chem. Ber. 1987, 120, 303 and
references cited therein.
(15) Selected examples: (a) Vella, P. A.; Beno, M.; Schultz, A. J .;
Williams, J . M. J . Organomet. Chem. 1981, 205, 71. (b) Huttner, G.;
Bejenke, V.; Mu¨ller, H.-D. Cryst. Struct. Commun. 1976, 5, 437. (c)
Benson, I. B.; Knox, S. A. R.; Stansfield, R. F. D.; Woodward, P. J .
Chem. Soc., Dalton Trans. 1981, 51.
(16) Traetteberg, M. J . Am. Chem. Soc. 1964, 86, 4265.

4986 Organometallics, Vol. 15, No. 23, 1996
Tamm et al.
Ta ble 1. Selected Bon d Dista n ces (Å) a n d
An gles (d eg) for 5
Sch em e 2
Mn1-C100
Mn1-C1
Mn1-C2
Mn1-C3
Mn1-C7
C100-O100
C1-C2
1.783(3)
2.109(4)
2.133(3)
2.147(3)
2.220(3)
1.150(4)
1.419(4)
C2-C3
C3-C3¢
C1-C4
C4-C5
C5-C6
C6-C7
C7-C7¢
1.422(5)
1.399(7)
1.524(5)
1.507(4)
1.322(5)
1.450(5)
1.409(7)
C100-Mn1-C100¢
Mn1-C6-C7
Mn1-O100-C100
90.5(2)
115.6(2)
177.4(3)
C5-C4-C1
C6-C5-C4
C5-C6-C7
110.0(2)
121.5(3)
125.7(3)
5, and replacement of the intramolecular alkene moiety
by other ligands only occurs under rather extreme
conditions (see below). We are currently investigating
the potential of this η2-C7H7-η5-C5H4-system in the
synthesis of new alkenylcyclopentadienyl complexes,18
as these donor-functionalized cyclopentadienyls belong
to the growing class of so-called hemilabile ligands,
which have received considerable interest in recent
years.19,20
Syn th eses of Sesqu ifu lva len e Com p lexes. As
mentioned above, the introduction of a ligand by an
alkene substitution reaction in 5 proves to be compara-
tively difficult. Whereas CpMn(CO)2(η2-cis-cyclooctene)
reacts readily with phosphines and isocyanides,14 no
reaction is observed if 5 is treated with triphenylphos-
phine or trimethyl phosphite in different solvents at
room temperature or under reflux conditions. However,
although stirring of 5 in neat trimethyl phosphite does
not give any product after 24 h, refluxing (120 °C) this
mixture for 60 min results in the almost quantitative
formation of 3b. In contrast, for the synthesis of 3c a
route similar to that reported for 3a has to be employed
with the respective ligand. Here, intramolecular coor-
dination of the cycloheptatrienyl unit as observed by
conversion of 3a into 5 is not possible due to the
separation of the five- and seven-membered rings by an
acetylenic C2 bridge. Formation of stable intermolecular
alkene complexes is prevented because of the presence
of more Lewis basic ligands such as phosphites and
phosphines.14 Complexes [(2)Mn(CO2)L]BF4 (8) are
obtained after hydride abstraction as red (8a ), greenish-
blue (8b), and blue (8c) crystals.
22
(Scheme 1).7,21 Lithiation of CpMn(CO)2PPh3 and
consecutive reaction with cycloheptatrienylium tet-
rafluoroborate, (C7H7)BF4, yields 3c. Hydride abstrac-
tion from complexes 3 is best achieved with triphenyl-
carbenium tetrafluoroborate, (Ph3C)BF4, and the cationic
sesquifulvalene complexes 4 are formed almost instantly
in CH2Cl2 solution. The complexes [(1)Mn(CO)2L]BF4
(4) are red-purple (4a ), greenish-blue (4b), and blue (4c)
crystalline compounds.
Str u ctu r a l Ch a r a cter iza tion of Sesqu ifu lva len e
Com p lexes 4b a n d 8b. The molecular structures of
the cations in 4b (top) and 8b (bottom) are depicted in
Figure 4.
For the syntheses of the higher “ethynylogues” 8b,c
(Scheme 2) the introduction of P(OMe)3 or PPh3 is best
achieved by irridation of 7a 7 in cyclohexane solution
The Cp rings are almost coplanar with the seven-
membered rings (dihedral angles of 2.4(4)° in 4b and
3.1(5)° in 8b). The inter-ring bond distance in 4b
(d(C1-C6) ) 1.467(8) Å) is only slightly shorter than
expected for a C(sp2)-C(sp2) single bond, and in 8b, the
C(sp)-C(sp) bond length (d(C13-C14) ) 1.200(14) Å)
indicates a triple bond (Table 2).23 Furthermore, the
C5 and C7 intra-ring bond lengths do not alternate
significantly. These observations indicate that the solid-
state structures of 4b and 8b are best described as
cymatrenyltropylium salts by the canonical forms A as
shown in Scheme 1 for 4b and Scheme 2 for 8b.
Comparison of the molecular structures of 4a 7 and 4b
reveals little sensitivity of the intra-ring C-C bond
distances upon the introduction of one phosphite ligand,
although the electronic and spectroscopic properties of
4a ,b differ significantly (see below).
(17) (a) Bauer, W.; Daub, J .; Maas, G.; Michna, M.; Rapp, K. M.;
Stezowski, J . J . Chem. Ber. 1982, 115, 99. (b) Herberhold, M.; Bauer,
K.; Milius, W. Z. Anorg. Allg. Chem. 1994, 620, 2108.
(18) (a) Okuda, J .; Zimmermann, K. H. Chem. Ber. 1989, 122, 1645.
(b) Okuda, J .; Zimmermann, K. H. Chem. Ber. 1990, 123, 1641. (c)
Okuda, J .; Zimmermann, K. H.; Herdtweck, E. Angew. Chem. 1991,
103, 446; Angew. Chem., Int. Ed. Engl. 1991, 30, 430. (d) Zimmermann,
K. H.; Pilato, R. S.; Horvath, I. T.; Okuda, J . Organometallics 1992,
11, 3935. (e) Lehmkuhl, H.; Na¨ser, J .; Mehler, G.; Keil, T.; Danowski,
F.; Benn, R.; Mynott, R.; Schroth, G.; Gabor, B.; Kru¨ger, C.; Betz, P.
Chem. Ber. 1991, 124, 441. (f) Alt, H. G.; Han, J . S.; Rogers, R. D. J .
Organomet. Chem. 1993, 445, 115. (g) Alt, H. G.; Han, J . S.; Thewalt,
U. J . Organomet. Chem. 1993, 456, 89. (h) Ma, Y; Bergman, R. G.
Organometallics 1994, 13, 2548.
(19) For recent reviews, see: (a) Okuda, J . Comments Inorg. Chem.
1994, 16, 185. (b) J utzi, P.; Dahlhaus, J . Coord. Chem. Rev. 1994, 137,
179. (c) J utzi, P.; Siemeling, U. J . Organomet. Chem. 1995, 500, 175.
(20) For recent publications, see: (a) Enders, M.; Rudolph, R.;
Pritzkow, H. Chem. Ber. 1996, 129, 459. (b) Foerstner, J .; Kettenbach,
R.; Goddard, R.; Butenscho¨n, H. Chem. Ber. 1996, 129, 319. (c)
Siemeling, U. Chem. Ber. 1995, 128, 1135. (d) Siemeling, U.; Vorfeld,
U.; Neumann, B.; Stammler, H.-G. Chem. Ber. 1995, 128, 481.
(21) Sterzo, C. L.; Miller, M. M.; Stille, J . K. Organometallics 1989,
8, 2331. (b) Sterzo, C. L.; Stille, J . K. Organometallics 1990, 9, 687.
(22) Barbeau, C.; Dichmann, K. S.; Ricard, L. Can. J . Chem. 1973,
51, 3027.
Sp ectr oscop ic P r op er ties of Sesqu ifu lva len e De-
r iva tives. The relative σ-donor/π-acceptor properties
(23) March, J erry Advanced organic chemistry; Wiley: New York,
1985; p 19.

Manganese(I) Sesquifulvalene Complexes
Organometallics, Vol. 15, No. 23, 1996 4987
Ta ble 3. IR Da ta for Com p lexes 3, 4, 7, a n d 8
a n d UV/Vis Da ta a n d F ir st Molecu la r
Hyp er p ola r iza bilities â of Sesqu ifu lva len e
Com p lexes 4 a n d 8
ν˜(CO),
âHRS
,
cm-1
λmax, nm
10-30 esu
k(CO),
∆ν˜,
a
compd A1 E/B1 N m-1 CH2Cl2 CH3CN cm-1 CH2Cl2 CH3CN
3a
4a
3b
4b
3c
4c
7a
8a
7b
8b
7c
8c
2020 1933 1556
2035 1964 1597
1950 1889 1489
1964 1911 1517
1930 1863 1453
1951 1900 1498
2025 1938 1564
2030 1952 1581
1950 1885 1486
1956 1886 1491
1936 1872 1465
1941 1873 1470
536
612
643
537
649
740
506
581
630
491
583
650
1110
870
45
54
29
40
50
44
38
53
320
39
1740
1740
1870
94
151
73
a
E for Mn(CO)3 complexes, B1 for Mn(CO)2L complexes (L )
P(OMe)3, PPh3).
andphotoelectron spectroscopy,28 and it is well accepted
that the π-acceptor capabilities decrease in the order
CO > P(OR)3 > PR3. This trend can be derived as well
by comparison of the IR spectra of a consecutive series
a , b, c of complexes 3, 4, 7, and 8, and the measured
carbonyl stretching frequencies along with the calcu-
lated Cotton-Kraihanzel29 CO force constants k(CO) are
depicted in Table 3. Substitution of L ) CO (a ) by the
weaker π-accepting ligands P(OMe)3 (b) and PPh3 (c)
leads to enhanced Mn(dπ) f CO(π*) back-bonding to
the remaining carbonyls and consequently lower k(CO)’s.
Complexes 4 exhibit greater CO force constants when
compared to the corresponding complexes 3 with identi-
cal Mn(CO)2L fragments, thus indicating that the ses-
quifulvalene ligand in 4 is a far better π-acceptor than
the cyclopentadienyl ligand in 3 due to π-conjugation
with the seven-membered tropylium ring. This also
holds for complexes 7 and 8, although the increase in
k(CO) is much less pronounced.
Sesquifulvalene complexes 4 and 8 are intensely
colored compounds. They show strong solvatochromic
behavior and their ultraviolet visible spectra are mark-
edly affected by varying the solvent, which usually is a
good indication of possible NLO activity.8,30 The lowest
energy band λmax (Table 3) is most strongly shifted upon
changing the solvent from dichloromethane to acetoni-
trile (∆ν˜ ranging from 320 cm-1 in 4c to 1870 cm-1 in
8c). Due to these hypsochromic shifts (negative solva-
tochromic behavior) we assign the lowest energy transi-
tion in these systems as being effectively the π to π*
CT transition,31 which is approximately (!) represented
by the canonical forms A (ground state) and B (excited
state) shown in Scheme 1 for 4 and Scheme 2 for 8.
F igu r e 4. ORTEP drawings of the cations in 4b (top) and
8b (bottom).
Ta ble 2. Selected Bon d Dista n ces (Å) a n d
An gles (d eg) for 4b a n d 8b
4b
8b
Mn-C100
Mn-C101
Mn-C1
Mn-C2
Mn-C3
Mn-C4
Mn-C5
Mn-P
1.771(7)
1.771(7)
2.144(6)
2.148(7)
2.155(7)
2.150(8)
2.138(7)
2.179(3)
1.154(7)
1.148(7)
1.428(9)
1.425(10)
1.467(8)
1.778(11)
1.756(10)
2.126(8)
2.152(8)
2.149(9)
2.131(9)
2.141(8)
2.166(2)
1.141(11)
1.162(10)
1.415(11)
1.414(11)
C100-O100
C101-O101
C1-C2
C1-C5
C1-C6
C1-C14
C2-C3
1.431(14)
1.426(12)
1.406(12)
1.400(13)
1.372(12)
1.390(12)
1.42(2)
1.39(2)
1.37(2)
1.35(2)
1.38(2)
1.399(10)
1.405(12)
1.406(10)
1.393(9)
1.401(9)
C3-C4
C4-C5
C6-C7
C6-C12
C6-C13
C7-C8
1.376(9)
1.387(10)
1.352(11)
1.386(10)
1.373(9)
C8-C9
C9-C10
C10-C11
C11-C12
C13-C14
1.393(13)
1.200(14)
Mn-C100-O100
Mn-C101-O101
C100-Mn-C101
C100-Mn-P
177.6(6)
178.6(7)
93.0(3)
92.2(2)
90.3(3)
176.6(10)
177.8(9)
91.2(5)
90.7(3)
89.0(3)
(26) (a) Keiter, R. L.; Verkade, J . G. Inorg. Chem. 1969, 8, 2115. (b)
Angelici, R. J .; Malone, M. Inorg. Chem. 1967, 6, 1731.
(27) (a) Wang, S. P.; Richmond, M. G.; Schwartz, M. J . Am. Chem.
Soc. 1992, 114, 7595. (b) Buchner, W.; Schenk, W. A. Inorg. Chem.
1984, 23, 132. (c) Bodner, G. M.; May, M. P.; McKinney, L. E. Inorg.
Chem. 1980, 19, 1951.
(28) Bancroft, G. M.; Dignard-Bailey, L.; Puddephatt, R. J . Inorg.
Chem. 1986, 25, 3675.
(29) Cotton, F. A.; Kraihanzel, C. S. J . Am. Chem. Soc. 1962, 84,
4432.
(30) (a) Paley, M. S.; Harris, J . M. J . Org. Chem. 1991, 56, 368. (b)
Green, M. L. H.; Marder, S. R.; Thompson, M. E.; Bandy, J . A.; Bloor,
D.; Kolinsky, P. V.; J ones, R. J . Nature 1987, 330, 360.
(31) (a) Reichardt, C. Chem. Rev. 1994, 94, 2319. (b) Reichardt, C.
Solvents and Solvent Effects in Organic Chemistry; VCH Publishers:
Weinheim, Germany, 1988. (c) Becker, H. G. O. Einfu¨hrung in die
Photochemie; Deutscher Verlag der Wissenschaften: Berlin, 1991.
C101-Mn-P
C1-C14-C13
C6-C13-C14
178.7(9)
176.7(9)
of CO, phosphites and phosphines have been studied24
by means of X-ray crystallography25 and IR,26 NMR,27
(24) Huheey, J .; Keiter, E.; Keiter, R. Anorganische Chemie; de
Gruyter: Berlin, New York, 1995; p 494 ff.
(25) (a) Liu, H.-Y.; Eriks, K.; Prock, A.; Giering, W. P. Organome-
tallics 1990, 9, 1758. (b) Plastas, H. J .; Stewart, J . M.; Grim, S. O. J .
Am. Chem. Soc. 1969, 91, 4326.

4988 Organometallics, Vol. 15, No. 23, 1996
Tamm et al.
Usually, extension of the conjugation path between an
electron donor and acceptor does increase the polariz-
ability significantly,1,8 which is in agreement with the
observation that complexes 8 generally exhibit greater
solvatochromic behavior than complexes 4.
membered tropylium ring by the Cr(CO)3 fragment
obviously induces an additional contribution due to
ligand-to-metal charge transfer. This observation has
to be taken into account for the future design of related
NLO chromophores.
In summary, we have presented manganese(I) ses-
quifulvalene complexes as new NLO chromophores,
whose electronic and optical properties can be easily and
efficiently tuned by ligand substitution reactions. This
concept could be extended to the introduction of readily
available chiral phosphines leading to optically active
compounds, which will crystallize in noncentrosymmet-
ric space groups and thus fulfill a crucial requirement
for the observation of macroscopic NLO effects.39
As mentioned above, the color of the sesquifulvalene
complexes strongly depends on the nature of the ligand
L in the Mn(CO)2L fragment changing from red-purple
in 4a /8a to greenish-blue in 4b/8b to deep blue in 4c/
8c. This represents an alternative spectrochemical
series32 in which significant bathochromic shifts (red
shifts)33 are observed for λmax upon substitution of CO
by the less π-accepting ligands trimethyl phosphite and
triphenylphosphine (Table 3). Decreasing the π-accep-
tor capability of the ligand L leaves the metal fragment
more electron rich thus increasing its donor strength,
which reduces the energy difference between the two
limiting resonance structures A and B (Schemes 1 and
2) or in other words decreases the HOMO/LUMO energy
gap of the corresponding π to π* CT excitation, respec-
tively.34
The succesful tuning of the electronic and optical
properties of 4a and 8a 7 encouraged us to measure the
first molecular hyperpolarizabilities using the hyper
Raleigh scattering technique.13 The first molecular
hyperpolarizabilities â of all sesquifulvalene complexes
4 and 8 were determined in dichloromethane and
acetonitrile solutions using p-nitroaniline as external
standard, and the results are shown in Table 3. The â
values strongly depend on the solvent polarity, which
is especially pronounced for complexes 8 exhibiting
much greater solvatochromic behavior than complexes
4 (see above). These differences can be rationalized by
resonance enhancement, which occurs when the fre-
quency of the charge-transfer excitation is close to the
frequency of the stimulating laser or close to the doubled
frequency. However, it should be noted that in our case
the simple two-level model9 is not a versatile tool for
the calculation of the static hyperpolarizability âo as the
frequency-doubled scattered light is still in the region
of very strong absorption. Furthermore, as expressed
by eq 1, âo itself does depend on the solvent polarity
and λmax derived thereof.35 Separation of resonance
enhancement contributions and influences of solvent
polarity would require the determination of â at a
different basic laser wavelength.
Exp er im en ta l Section
All operations were performed in an atmosphere of dry
argon by using Schlenk and vacuum techniques. Solvents
were dried by standard methods and distilled prior to use.
NMR spectra were recorded on a Bruker AM 250 (250 MHz)
instrument. Infrared spectra were taken on a Perkin-Elmer
983 instrument. Elemental analyses (C, H, N) were performed
at the Freie Universita¨t Berlin on a Heraeus CHN-Rapid
elemental analyzer. Mass spectra were recorded on a Varian
MAT 711 instrument, and UV/vis spectra, on a Perkin-Elmer
Lambda 9 UV/vis/near-IR spectrophotometer using 10-3
M
solutions. Photochemical reactions were performed with a TQ
150 high-pressure mercury vapor lamp (Hanau). 3a ,7 4a ,7 and
622 were synthesized as previously described. Tropylium
tetrafluoroborate was prepared by literature methods.40 Triph-
enylcarbenium tetrafluoroborate, trimethyl phosphite, and
triphenylphosphine were received from Aldrich and used
without further purification.
Syn th esis of 3b. A 500 mg (1.9 mmol) amount of 5 was
dissolved in 10 mL of P(OMe)3, and the mixture was heated
at 120 °C for 60 min. Excess phosphite was removed in vacuo,
and the yellow, oily residue was chromatographed on silica
(4% H2O) using hexane/dichloromethane (1:1) as eluent. 3b
was obtained as a yellow oil, 510 mg (70%). 1H NMR (CDCl3,
250 MHz): δ 6.64 (t, 2H, C7 CH), 6.16 (dm, 2H, C7 CH), 5.22
(m, 2H, C7 CH), 4.58 (t, 2H, C5 CH), 4.42 (t, 2H, C5 CH), 3.55
3
(d, J PC ) 12 Hz, 9H, POCH3), 2.42 (t, 1H, C7 CH). 13C{1H}
NMR (CDCl3, 62.90 MHz): δ 229.8 (d, 1J PC ) 39 Hz, CO), 130.9
(C7 CH), 125.4 (C7 CH), 124.3 (C7 CH), 105.4 (C5 C-1), 80.7 (C5
CH), 80.2 (C5 CH), 51.4 (POCH3), 38.0 (C7 C-7). IR (CH2Cl2):
ν(CO) 1950, 1889 cm-1
. MS (EI, 70 eV): m/ z (relative
intensity) 390 (30.5) [M+], 359 (8.7) [(M - OCH3)+], 334 (60.9)
[(M - 2CO)+], 210 (100) [(M - 2CO - P(OMe)3)+], 155 (14.3)
[C12H11+]. Anal. Calcd for C17H20MnO5P (Mr ) 390.25): C,
52.32; H, 5.17. Found: C, 52.67; H, 5.17.
The â values reported here are reasonably high com-
pared to organic36 and organometallic8,34,37 compounds
of comparable chromophore length. However, the het-
erobimetallic iron-chromium complexes reported by
Heck et al.8 exhibit significantly higher hyperpolariz-
abilities38 indicating that complexation of the seven-
Syn th esis of 3c. A solution of 6 (2.48 g, 5.7 mmol) in 50
mL of thf was treated dropwise with sec-BuLi (4.5 mL of a 1.3
M solution in hexane, 5.9 mmol) at -78 °C. After the solution
was stirred for 45 min at -78 °C, tropylium tetrafluoroborate
(1.3 g, 7.3 mmol) was added as a solid and the reaction mixture
was allowed to warm to room temperature. Stirring was
continued for 60 min, and the solvent was removed in vacuo.
Chromatography on silica (4% H2O) with hexane/dichlo-
romethane (1:1) yielded 2.57 g of a yellow solid, which
(32) Lever, A. B. P. Inorganic Electronic Spectroscopy, 2nd ed.;
Elsevier: New York, 1986.
(33) Note the alleged contradiction: In the order for instance from
4a to 4c λmax is red shifted and consequently the color changes from
red to blue.
1
according to its H NMR spectra was an unseparable mixture
(34) Calabrese, J . C.; Cheng, L.-T.; Green, J . C.; Marder, S. R.; Tam,
W. J . Am. Chem. Soc. 1991, 113, 7227.
(35) Sta¨helin, M.; Burland, D. M.; Rice, J . E. Chem. Phys. Lett. 1992,
191, 245.
(36) (a) Cheng, L.-T.; Tam, W.; Stevenson, S. H.; Meredith, G. R.;
Rikken, G.; Marder, S. R. J . Phys. Chem. 1991, 95, 10631. (b) Cheng,
L.-T.; Tam, W.; Marder, S. R.; Stiegman, A. E.; Rikken, G.; Spangler,
C. W. J . Phys. Chem. 1991, 95, 10643.
(37) (a) Kanis, D. R.; Ratner, M. A.; Marks, T. J . Chem. Rev. 1994,
94, 195. (b) Yuan, Z.; Taylor, N. J .; Sun, Y.; Marder, T. B.; Williams,
I. D.; L.-T.; Cheng J . Organomet. Chem. 1993, 449, 27. (c) Loucif-Saibi,
R.; Delaire, J . A.; Bonazzola, L. Chem. Phys. 1992, 167, 369.
(38) For complex {CpFe[(η5-C5H4)CtC(η7-C7H6)Cr(CO)3}BF4 incor-
porating the sesquifulvalene ligand 2, â ) 570 × 10-30 esu (âo ) 105
× 10-30 esu) was reported.8
(39) (a) Dias, A. R.; Garcia, M. H.; Rodrigues, J . C.; Green, M. L.
H.; Kuebler, S. M. J . Organomet. Chem. 1994, 475, 241.(b) Dias, A.
R.; Garcia, M. H.; Robalo, M. P.; Green, M. L. H.; Lai, K. K.; Pulham,
A. J .; Kuebler, S. M. J . Organomet. Chem. 1993, 453, 241. (c) Togni,
A.; Rihs, A. Organometallics 1993, 12, 3368.
(40) Asao, T.; Oda, M. In Methoden der Organischen Chemie
(Houben-Weyl); Kropf, H., Ed.; Georg Thieme Verlag: Stuttgart,
Germany, 1985; Vol. V/2c, p 49.

Manganese(I) Sesquifulvalene Complexes
Organometallics, Vol. 15, No. 23, 1996 4989
2
of 6 and 3c (1:4.2). This mixture was used for subsequent
hydride abstraction without further purification. Yield: 69%
(based on 3c in the product mixture). 1H NMR (CDCl3, 250
MHz): δ 7.40 (m, 15H, PC6H5), 6.68 (m, 2H, C7 CH), 6.19 (m,
2H, C7 CH), 5.34 (m, 2H, C7 CH), 4.41 (s br, 2H, C5 CH), 4.05
(s br, 2H, C5 CH), 2.45 (s br, 1H, C7 CH). IR (CH2Cl2): ν(CO)
13C NMR (CDCl3, 62.90 MHz): δ 229.1 (d, J PC ) 37 Hz, CO),
131.0 (C7 CH), 124.8 (C7 CH), 123.0 (C7 CH), 89.3 (CtC), 86.0
(C5 C-1), 85.4 (C5 CH), 80.4 (C5 CH), 74.6 (CtC), 51.5 (POCH3),
32.1 (C7 C-7). IR (CH2Cl2): ν(CO) 1950, 1885 cm-1. MS (EI,
70 ev): m/z (relative intensity) 414 (21.7) [M+], 358 (80.9) [(M
- 2CO)+], 234 (72.2) [(M - 2CO - P(OMe)3)+], 93 (100)
[P(OMe)2+].
1930, 1863 cm-1
.
Syn th esis of 7c. 7a (1.00 g, 3.1 mmol) and PPh3 (1.24 g,
4.71 mmol) dissolved in 220 mL of cyclohexane were irradiated
in a photoreactor for 1 h (TLC control). The solvent was
removed in vacuo from the brownish solution. The crude
product was purified chromatographically on silica (4% H2O)
using hexane/dichloromethane (2:1) as eluent. After removal
of the solvent 7c was obtained as a yellow solid, 795 mg (46%).
1H NMR (CDCl3, 250 MHz): δ 7.43 (m, 15H, PC6H5), 6.66 (t,
2H, C7 CH), 6.14 (dm, 2H, C7 CH), 5.32 (m, 2H, C7 CH), 4.50
(t, 2H, C5 CH), 4.02 (t, 2H, C5 CH), 2.53 (t, 1H, C7 CH). 13C
NMR (CDCl3, 62.90 MHz): δ 232.1 (d, 2J PC ) 25 Hz, CO), 137.7
Syn th esis of 4b. To a solution of 3b (220 mg, 0.6 mmol)
in 10 mL of CH2Cl2 was added triphenylcarbenium tetrafluo-
roborate (190 mg, 0.6 mmol) as a solid. The solution im-
mediately turned green-blue, and stirring was continued for
60 min. After addition of 90 mL of diethyl ether the greenish-
blue precipitate was isolated by filtration and washed with
diethyl ether, 205 mg (75%): Mp 178-181 °C. 1H NMR (CD3-
CN, 250 MHz): δ 8.60 (m, 2H, C7 CH), 8.44 (m, 4H, C7 CH),
5.84 (t, 2H, C5 CH), 5.30 (t, 2H, C5 CH), 3.50 (d, 3J PC ) 12 Hz,
9H, POCH3). 13C NMR (CD3CN, 62.90 MHz): δ 227.7 (d, 2J PC
) 41 Hz, CO), 169.6 (C7 C-7), 150.6 (2 × C7 CH), 147.6 (C7
1
2
(d, J PC ) 41 Hz, P-C), 133.0 (d, J PC ) 11 Hz, P-C-C), 131.0
(C7 CH), 129.5 (P-C-C-C-C), 128.1 (d, 3J PC ) 10 Hz, P-C-
C-C), 124.7 (C7 CH), 123.4 (C7 CH), 89.9 (CtC), 85.5 (C5 CH),
82.5 (C5 CH), 80.7 (C5 C-1), 75.1 (CtC), 32.3 (C7 C-7). IR (CH2-
2
CH), 91.2 (C5 C-1), 88.4 (C5 CH), 88.1 (C5 CH), 53.1 (d, J PC
)
4 Hz, POCH3). IR (CH2Cl2): ν(CO) 1964, 1911 cm-1
. MS
(FAB): m/z (relative intensity) 389 (100) [M+], 333 (28.7) [(M
- 2CO)+], 209 (28.2) [(M - 2CO - P(OMe)3)+]. UV/vis (CH2-
Cl2): ν (ꢀ) 264 (21 000), 369 (20 800), 612 (9000) nm (L mol-1
cm-1). UV/vis (CH3CN): ν (ꢀ) 261 (18 800), 361 (17 100), 581
(6700) nm (L mol-1 cm-1). Anal. Calcd for C17H19BF4MnO5P
(Mr ) 476.05): C, 42.89; H, 4.02. Found: C, 42.79; H, 4.35.
Cl2): ν(CO) 1936, 1872 cm-1
. MS (EI, 70 ev): m/z (relative
intensity) 552 (10.0) [M+], 496 (100) [(M - 2CO)+], 262 (26.1)
[PPh3+], 234 (29.1) [(M - 2CO - PPh3)+]. Anal. Calcd for
C
34H26MnO2P (Mr ) 552.49): C, 73.92; H, 4.74. Found: C,
71.36; H, 5.05.
Syn th esis of 4c. A mixture (1:4.2) of 6 and 3c (1.38 g, 2.1
mmol of 3c) was dissolved in 20 mL of CH2Cl2, and triphenyl-
carbenium tetrafluoroborate (700 mg, 2.1 mmol) was added
as a solid. The solution immediately turned deep blue, and
stirring was continued for 60 min. After addition of 100 mL
of diethyl ether the blue precipitate was isolated by filtration
and washed with diethyl ether, 980 mg (76%): Mp 209-212
°C. 1H NMR (CD3CN, 250 MHz): δ 8.37-8.10 (m, 6H, C7 CH),
7.36 (m, 15H, PC6H5), 5.76 (t, 2H, C5 CH), 5.10 (t, 2H, C5 CH).
13C NMR (CD3CN, 62.90 MHz): δ 230.6 (d, 2J PC ) 20 Hz, CO),
169.5 (C7 C-7), 150.4 (C7 CH), 150.2 (C7 CH), 146.9 (C7 CH),
Syn th esis of 8b. To a solution of 7b (220 mg, 0.5 mmol)
in 20 mL of CH2Cl2 was added triphenylcarbenium tetrafluo-
roborate (175 mg, 0.5 mmol) as a solid. The solution im-
mediately turned blue, and stirring was continued for 30 min.
After addition of 100 mL of diethyl ether the greenish-blue
precipitate was isolated by filtration and washed with diethyl
ether, 220 mg (83%): Mp 94-96 °C (dec). 1H NMR (CD3CN,
250 MHz): δ 8.78 (m, 6H, C7 CH), 5.28 (t, 2H, C5 CH), 4.88 (t,
3
2H, C5 CH), 3.56 (d, J PC ) 11 Hz, 9H, POCH3). 13C NMR
2
(CD3CN, 62.90 MHz): δ 229.1 (d, J PC ) 36 Hz, CO), 154.8
(C7 CH), 153.7 (C7 CH), 153.0 (C7 CH and C7 C-7), 112.8 (C5
C-1), 93.5 (CtC), 90.7 (C5 CH), 84.7 (C5 CH), 72.1 (CtC), 52.6
1
2
137.1 (d, J PC ) 42 Hz, P-C) 133.9 (d, J PC ) 8 Hz, P-C-C),
131.2 (P-C-C-C-C), 129.5 (d, 3J PC ) 6 Hz, P-C-C-C), 92.2
(C5 C-1), 90.1 (C5 CH), 88.4 (C5 CH). IR (CH2Cl2): ν(CO) 1951,
(POCH3). IR (CH2Cl2): ν(CO) 1956, 1886 cm-1
. MS (FAB):
m/z (relative intensity) 413 (31.2) [M+], 385 (27.8) [(M - CO)+],
358 (20.1) [(M - 2CO)+], 233 (19.2) [(M - 2CO - P(OMe)3)+],
178 (29.3) [C14H10+], 93 (100) [P(OMe)2+]. UV/vis (CH2Cl2): ν
(ꢀ) 271 (14 000), 410 (12 400), 649 (5800) nm (L mol-1 cm-1).
UV/vis (CH3CN): ν (ꢀ) 266 (12 700), 392 (9700), 583 (4200) nm
1900 cm-1
. MS (FAB): m/ z (relative intensity) 527 (15.3)
[M+], 471 (20.6) [(M - 2CO)+], 154 (100) [C12H10+]. UV/vis
(CH2Cl2): ν (ꢀ) 261 (27 600), 378 (21 000), 643 (7200) nm (L
mol-1 cm-1). UV/vis (CH3CN): ν (ꢀ) 258 (20 990), 373 (15 800),
630 (5020) nm (L mol-1 cm-1). Anal. Calcd for C32H25BF4-
MnO2P (Mr ) 614.26): C, 62.57; H, 4.10. Found: C, 62.62;
H, 5.13.
(L mol-1 cm-1). Anal. Calcd for C19H19BF4MnO5P (Mr
500.08): C, 45.63; H, 3.83. Found: C, 45.60; H, 4.62.
)
Syn th esis of 8c. To a solution of 7c (600 mg, 1.1 mmol) in
20 mL of CH2Cl2 was added triphenylcarbenium tetrafluo-
roborate (360 mg, 1.1 mmol) as a solid. The solution im-
mediately turned blue, and stirring was continued for 30 min.
After addition of 100 mL of diethyl ether, a blue solid
precipitated. Filtration and washing with diethyl ether yielded
8c as a deep blue solid, 560 mg (80%): Mp 125 °C (dec). 1H
NMR (CD3CN, 250 MHz): δ 8.76 (m, 4H, C7 CH), 8.60 (m,
2H, C7 CH), 7.44 (m, 15H, PC6H5), 5.12 (t, 2H, C5 CH), 4.80 (t,
Syn th esis of 5. 3a (1.0 g, 3.4 mmol) dissolved in 200 mL
of cyclohexane was irradiated in a photoreactor for 10 h. The
solvent was removed in vacuo, and the brownish-yellow solid
was purified by sublimation (0.01 mbar, 80 °C) and recrystal-
lized from hexane to give 5 as yellow crystals, 550 mg (61%):
Mp 148-151 °C. 1H NMR (CDCl3, 250 MHz): δ 6.70 (m, 2H,
C7 CH), 6.05 (t, 2H, C7 CH), 4.57 (t, 2H, C5 CH), 4.08 (t, 2H,
C5 CH), 3.53 (t, 2H, C7 CH), 3.20 (t, 1H, C7 CH). 13C{1H} NMR
(CDCl3, 62.90 MHz): δ 235.3 (CO), 135.3 (C7 CH), 135.0 (C5
C-1), 131.2 (C7 CH), 90.9 (C5 CH), 80.6 (C5 CH), 58.2 (C7 CH),
33.4 (C7 C-7). IR (cyclohexane): ν(CO) 1968, 1913 cm-1. MS
(EI, 70 eV): m/ z (relative intensity) 266 (17.1) [M+], 238 (5.3)
2
2H, C5 CH). 13C NMR (CD3CN, 62.90 MHz): δ 233.3 (d, J PC
) 24 Hz, CO), 154.7 (C7 CH), 153.5 (C7 CH), 152.9 (C7 C-7),
152.5 (C7 CH), 135.9 (s br, P-C), 133.7 (s br, P-C-C), 131.2 (s
br, P-C-C-C-C), 129.3 (s br, P-C-C-C), 114.1 (C5 C-1),
94.7 (CtC), 91.5 (C5 CH), 86.9 (C5 CH), 73.5 (CtC). IR (CH2-
[(M - CO)+], 210 (100) [(M - 2CO)+]. Anal. Calcd for C14H11
-
Cl2): ν(CO) 1941, 1873 cm-1
.
MS (FAB): m/z (relative
MnO2 (Mr ) 266.18): C, 63.17; H, 4.17. Found: C, 63.33; H,
intensity) 551 (5.7) [M+], 495 (10.9) [(M - 2CO)+]. UV/vis
(CH2Cl2): ν (ꢀ) 425 (13 900), 740 (4700) nm (L mol-1 cm-1).
UV/vis (CH3CN): ν (ꢀ) 405 (13 200), 650 (4200) nm (L mol-1
cm-1). Anal. Calcd for C34H25BF4MnO2P (Mr ) 638.29): C,
63.98; H, 3.95. Found: C, 63.69; H, 4.56.
4.22.
Syn th esis of 7b. 7a (750 mg, 2.4 mmol) and 440 mg (0.42
mL, 3.5 mmol) of P(OMe)3 dissolved in 250 mL of cyclohexane
were irradiated in a photoreactor for 2 h. The solvent was
removed in vacuo, and the crude product was purified chro-
matographically on silica (4% H2O) with hexane/dichlo-
romethane (2:1) as eluent. After removal of the solvent 7b
was obtained as a dark yellow oil, 280 mg (29%). 1H NMR
(CDCl3, 250 MHz): δ 6.64 (t, 2H, C7 CH), 6.14 (dm, 2H, C7
CH), 5.30 (m, 2H, C7 CH), 4.80 (t, 2H, C5 CH), 4.45 (t, 2H, C5
X-r a y St r u ct u r a l Det er m in a t ion of 4b , 5, a n d 8b .
Single crystals are stable under ambient conditions and were
mounted on glass pins for data collection (room temperature,
Enraf-Nonius Turbo-CAD4 single-crystal diffractometer, rotat-
ing anode generator, Cu KR radiation, ω-scan mode). Unit cell
dimensions were determined from the angular setting of 25
3
CH), 3.56 (d, J PC ) 12 Hz, 9H, POCH3), 2.60 (t, 1H, C7 CH).

4990 Organometallics, Vol. 15, No. 23, 1996
Ta ble 4. Cr ysta llogr a p h ic Da ta for 4b, 5, a n d 8b
Tamm et al.
4b
5
8b
cryst size, mm
formula
fw
0.65 × 0.04 × 0.02
C17H19BF4MnO5
476.04
0.40 × 0.35 × 0.07
C14H11MnO2
266.17
0.20 × 0.15 × 0.05
C19H19BF4MnO5P
500.07
wavelength, Å
cryst system
space group
a, Å
1.54176
triclinic
P1h (No. 2)
6.686(2)
1.54176
1.54176
orthorhombic
Pnma (No. 62)
6.455(1)
monoclinic
P21/c (No. 14)
10.9676(7)
12.918(1)
b, Å
8.761(3)
11.911(2)
c, Å
17.276(8)
84.36(11)
88.09(6)
86.23(8)
1004.5(7)
2
1.574
6.685
484
14.653(1)
15.600(1)
R, deg
â, deg
93.50(2)
γ, deg
V, Å3
1126.6(3)
4
1.569
9.400
544
2206.0(3)
4
1.509
6.121
1020
Z
F
calc, g/cm3
µ, mm-1
F(000)
θ range, deg
2.57 e θ e 60.05
0 e h e 7
-9 e k e 9
-19 e l e 19
0.890, 0.999
3278
4.78 e θ e 59.84
0 e h e 7
0 e k e 13
-16 e l e 16
0.728, 0.995
1729
4.04 e θ e 59.97
-12 e h e 12
-1 e k e 14
-17 e l e 2
0.738, 0.996
4376
index ranges
T
min, Tmax
rflns collcd
independent rflns
no. of params
2983 [R(int) ) 0.0329]
884 [R(int) ) 0.0226]
3279 [R(int) ) 0.0373]
314
105
293
GOF on F2
1.027
1.071
1.031
R [I > 2σ(I)]
0.0649
0.1821
<0.001
0.688 and -0.426
0.0393
0.1064
<0.001
0.447 and -0.524
0.0820
0.2654
0.006
0.803 and -0.596
wR2 (all data)
∆/σ (max)
largest diff peak and hole, e/Å3
reflections. Crystal data are given in Table 4. Semi-empirical
absorption correction (ψ-scan) was applied. Structures were
solved with direct methods (SHELXS 86)41 and refined with
standard methods (refinement against F2 with SHELXL 93).42
For 4b and 5, hydrogen atoms were refined isotropically,
except for the methyl groups in 4b, which were refined in the
riding model (SHELXL 93).42 In 8b all hydrogen atoms were
refined in the riding model. In 4b and 8b, the fluorine atoms
in the tetrafluoroborate anions exhibit very high displacement
parameters probably indicating excessive thermal motion or
disorder, which is not resolved. Crystals of 8b showed reduced
diffraction power compared to 4b and 5 resulting in a higher
R value and larger standard deviations obtained in the
refinement.
as external reference (â(CH2Cl2) ) 16.9 × 10-30 esu, â(CH3-
CN) ) 29.2 × 10-30 esu).35 The general experimental setup is
described in ref 13b. Further experimental details will be
published elsewhere.43
Ack n ow led gm en t. This work was financially sup-
ported by the Deutsche Forschungsgemeinschaft (Grants
Ta 189/1-1 and Ta 189/1-3) and the Fonds der Chemis-
chen Industrie. We wish to thank Prof. Dr. F. E. Hahn
for his generous support.
Su p p or tin g In for m a tion Ava ila ble: Tables of X-ray
data, positional and thermal parameters, and bond distances
and angles (24 pages). Ordering information is given on any
current masthead page.
Hyp er Ra leigh Sca tter in g. The experiments were per-
formed at a wavelength of 1064 nm with a mode-locked
Q-switch Nd:YAG laser (Quantronix 5216). Solutions of
p-nitroaniline in acetonitrile and dichloromethane were used
OM960571T
(41) Sheldrick, G. M. SHELXS 86, Program for the Solution of
Crystal Structures; Universita¨t Go¨ttingen: Go¨ttingen, Germany, 1986.
(42) Sheldrick, G. M. SHELXL 93, Program for the Refinement of
Crystal Structures; Universita¨t Go¨ttingen: Go¨ttingen, Germany, 1993.
(43) J entzsch, T.; Werncke, W.; Tamm, M. Manuscript in prepara-
tion.