Primary and secondary phosphine complexes of iron porphyrins and ruthenium phthalocyanine: Synthesis, structure, and P-H bond functionalization

Article abstract of DOI:10.1021/ic800484k

Reduction of [Fe^III(Por)Cl] (Por = porphyrinato dianion) with Na₂S₂O₄ followed by reaction with excess PH₂Ph, PH₂Ad, or PHPh₂ afforded [Fe ^II(F₂₀-TPP)(PH₂Ph)₂] (1a), [Fe ^II(F₂₀-TPP)(PH₂Ad)₂] (1b), [Fe ^II(F₂₀-TPP)(PHPh₂)₂] (2a), and [Fe^II(2,6-Cl₂TPP)(PHPh₂)₂] (2b). Reaction of [Ru^II(Pc)(DMSO)₂] (Pc = phthatocyaninato dianion) with PH₂Ph or PHPh₂ gave [Ru^II(Pc) (PH₂Ph)₂] (3a) and [Ru^II(Pc)(PHPh ₂)₂] (4). [Ru^II(Pc)(PH₂Ad) ₂] (3b) and [Ru^II(Pc)(PH₂Bu^t) ₂] (3c) were isolated by treating a mixture of [Ru ^II(Pc)(DMSO)₂] and O=PCl₂Ad or PCl ₂Bu^t with LiAlH₄. Hydrophosphination of CH ₂=CHR (R = CO₂Et, CN) with [Ru^II(F ₂₀-TPP)(PH₂Ph)₂] or [Ru^II(F ₂₀-TPP)(PHPh₂)₂] in the presence of ^tBuOK led to the isolation of [Ru^II(F₂₀-TPP) (P(CH₂CH₂R)₂Ph)₂] (R = CO ₂Et, 5a; CN, 5b) and [Ru^II(F₂₀-TPP)(P(CH ₂CH₂R)Ph₂)₂] (R = CO₂Et, 6a; CN, 6b). Similar reaction of 3a with CH₂=CHCN or Mel gave [Ru^II(Pc)(P(CH₂CH₂CN)₂Ph) ₂] (7) or [Ru^II(Pc)(PMe₂Ph)₂] (8). The reactions of 4 with CH₂=CHR (R = CO₂Et, CN, C(O)Me, P(O)(OEt)₂, S(O)₂Ph), CH₂=C(Me)CO ₂Me, CH(CO₂Me)=CHCO₂Me, Mel, BnCl, and RBr (R = ⁿBu, CH₂=CHCH₂, MeC≡CCH₂, HC≡CCH₂) in the presence of ^tBuOK afforded [Ru ^II(Pc)(P(CH₂CH₂R)Ph₂)₂] (R = CO₂Et, 9a; CN, 9b; C(O)Me, 9c; P(O)(OEt)₂, 9d; S(O)₂Ph, 9e), [Ru^II(Pc)(P(CH₂CH(Me)CO ₂Me)Ph₂)₂] (9f), [RU^II(PC) (P(CH(CO₂Me)CH₂CO₂Me)Ph₂) ₂] (9g), and [Ru^II(Pc)(PRPh₂)₂] (R = Me, 10a; Buⁿ, 10b; Bn, 10c; CH₂CH=CH₂, 10d; CH₂C≡CMe, 10e; CH=C=CH₂, 10f). X-ray crystal structure determinations revealed Fe-P distances of 2.2597(9) (1a) and 2.309(2) A(2b·2CH₂Cl₂) and Ru-P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) A(5b·2CH₂Cl₂). Both the crystal structures of 3b and 4 feature intermolecular C-H ... π interactions, which link the molecules into 3D and 2D networks, respectively.

Full text of DOI:10.1021/ic800484k

Inorg. Chem. 2008, 47, 9166-9181
Primary and Secondary Phosphine Complexes of Iron Porphyrins and
Ruthenium Phthalocyanine: Synthesis, Structure, and P-H Bond
Functionalization
Jie-Sheng Huang,* Guang-Ao Yu, Jin Xie, Kwok-Ming Wong, Nianyong Zhu, and Chi-Ming Che*
Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular
Technology for Drug DiscoVery and Synthesis, The UniVersity of Hong Kong,
Pokfulam Road, Hong Kong
Received March 17, 2008
Reduction of [FeIII(Por)Cl] (Por ) porphyrinato dianion) with Na2S2O4 followed by reaction with excess PH2Ph,
PH2Ad, or PHPh2 afforded [FeII(F20-TPP)(PH2Ph)2] (1a), [FeII(F20-TPP)(PH2Ad)2] (1b), [FeII(F20-TPP)(PHPh2)2] (2a),
and [FeII(2,6-Cl2TPP)(PHPh2)2] (2b). Reaction of [RuII(Pc)(DMSO)2] (Pc ) phthalocyaninato dianion) with PH2Ph or
PHPh2 gave [RuII(Pc)(PH2Ph)2] (3a) and [RuII(Pc)(PHPh2)2] (4). [RuII(Pc)(PH2Ad)2] (3b) and [RuII(Pc)(PH2But)2] (3c)
were isolated by treating a mixture of [RuII(Pc)(DMSO)2] and OdPCl2Ad or PCl2But with LiAlH4. Hydrophosphination
of CH2dCHR (R ) CO2Et, CN) with [RuII(F20-TPP)(PH2Ph)2] or [RuII(F20-TPP)(PHPh2)2] in the presence of tBuOK
led to the isolation of [RuII(F20-TPP)(P(CH2CH2R)2Ph)2] (R ) CO2Et, 5a; CN, 5b) and [RuII(F20-TPP)(P(CH2CH2R)Ph2)2]
(R ) CO2Et, 6a; CN, 6b). Similar reaction of 3a with CH2dCHCN or MeI gave [RuII(Pc)(P(CH2CH2CN)2Ph)2] (7)
or [RuII(Pc)(PMe2Ph)2] (8). The reactions of 4 with CH2dCHR (R ) CO2Et, CN, C(O)Me, P(O)(OEt)2, S(O)2Ph),
n
CH2dC(Me)CO2Me, CH(CO2Me)dCHCO2Me, MeI, BnCl, and RBr (R ) Bu, CH2dCHCH2, MeCtCCH2,
HCtCCH2) in the presence of tBuOK afforded [RuII(Pc)(P(CH2CH2R)Ph2)2] (R ) CO2Et, 9a; CN, 9b; C(O)Me, 9c;
P(O)(OEt)2, 9d; S(O)2Ph, 9e), [RuII(Pc)(P(CH2CH(Me)CO2Me)Ph2)2] (9f), [RuII(Pc)(P(CH(CO2Me)CH2CO2Me)Ph2)2]
(9g), and [RuII(Pc)(PRPh2)2] (R ) Me, 10a; Bun, 10b; Bn, 10c; CH2CHdCH2, 10d; CH2CtCMe, 10e; CHdCdCH2,
10f). X-ray crystal structure determinations revealed Fe-P distances of 2.2597(9) (1a) and 2.309(2) Å (2b· 2CH2Cl2)
and Ru-P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) Å (5b· 2CH2Cl2). Both the
crystal structures of 3b and 4 feature intermolecular C-H· · ·π interactions, which link the molecules into 3D and
2D networks, respectively.
Introduction
hemoproteins,2 the employment of phosphines to stabilize
rhodium complexes in low oxidation states,3 and the design
of multiporphyrinic arrays based on the coordination of
phosphines to metalloporphyrins.5 Conventionally, tertiary
phosphine ligands are employed in the chemistry of metal-
loporphyrin complexes. Only until recently has the binding
behavior of primary and secondary phosphines (PH2R and
PHR2) to metalloporphyrins been reported in the literature;
the earliest example is a work by Sanders and co-workers,6
reporting the in situ formation of [RuII(Por)(CO)(PH2-
(CtCPh))] and [RuII(Por)(PH2(CtCPh))2], together with the
Phosphines have long been used as axial ligands in the
development of metalloporphyrin chemistry1 and continue
to receive considerable attention,2-5 including the use of
phosphine complexes of iron porphyrins as models of
* Authors to whom correspondence should be addressed. E-mail:
jshuang@hkucc.hku.hk (J.-S.H.); cmche@hku.hk (C.-M.C.).
(1) For reviews, see: (a) Buchler, J. W. In Porphyrins and Metallopor-
phyrins; Smith, K. M., Ed.; Elsevier: Amsterdam, 1975; p 157. (b)
Buchler, J. W. In The Porphyrins; Dolphin, D., Ed.; Academic: New
York, 1978; Vol. 1, p 389. (c) Mashiko, T.; Dolphin, D. In
ComprehensiVe Coordination Chemistry; Wilkinson, G., Gillard, R. D.,
McCleverty, J. A., Eds.; Pergamon: Oxford, U.K., 1987; Vol. 2, p
813. (d) Buchler, J. W.; Dreher, C.; Kunzel, F. M. Struct. Bonding
(Berlin) 1995, 84, 1. (e) Sanders, J. K. M.; Bampos, N.; Clyde-Watson,
Z.; Darling, S. L.; Hawley, J. C.; Kim, H.-J.; Mak, C. C.; Webb, S. J.
In The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard,
R., Eds.; Academic Press: San Diego, CA, 2000; Vol. 3, p 1.
(2) (a) Simonneaux, G. Coord. Chem. ReV. 1997, 165, 447. (b) Simon-
neaux, G.; Bondon, A. In The Porphyrin Handbook; Kadish, K. M.,
Smith, K. M., Guilard, R., Eds.; Academic Press: San Diego, CA,
2000; Vol. 5, p 299.
(3) Collman, J. P.; Boulatov, R. J. Am. Chem. Soc. 2000, 122, 11812.
9166 Inorganic Chemistry, Vol. 47, No. 20, 2008
10.1021/ic800484k CCC: $40.75  2008 American Chemical Society
Published on Web 09/19/2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
binding of a H2P-CtC- or H2P-CdC- group of a
nickel(II)- or zinc(II)-bound porphyrin ligand, respectively,
to ruthenium and rhodium porphyrins. These primary alkynyl
or alkenyl phosphine complexes are unstable in solution and
have not been isolated.6 We have recently prepared a number
of ruthenium porphyrin complexes of PH2R (R ) aryl or
alkyl) and PHPh2;7 most of these complexes can be isolated
in pure form.
phyrins, both of which contain a large, planar macrocyclic
π-conjugated ligand system. In contrast to the case of
metalloporphyrins, phosphine complexes of metallophtha-
locyanines are less developed.10
Herein, we report the isolation of iron(II) porphyrins
[FeII(Por)(PH2R)2] (1, R ) Ph, Ad (adamantyl)) and [FeII-
(Por)(PHPh2)2] (2) and ruthenium(II) phthalocyanines [RuII-
(Pc)(PH2R)2] (3, R ) Ph, Ad, But) and [RuII(Pc)(PHPh2)2]
(4). The functionalization of P-H bonds in these ruthenium
phthalocyanines and previously reported ruthenium porphyrin
analogues has been investigated, revealing that [RuII(F20-
TPP)(PH2Ph)2], [RuII(F20-TPP)(PHPh2)2], and their phthalo-
cyanine counterparts can undergo hydrophosphination reac-
tions with alkenes and P-alkylation reactions with haloalkanes.
This, to the best of our knowledge, contributes the first P-H
bond functionalization of primary or secondary phosphines
coordinated to a metalloporphyrin and a metallophthalocya-
nine.
Metalloporphyrins such as [M(Por)(PH2R)2] and [M(Por)-
(PHR2)2] could be useful precursors to (i) phosphido and
phosphinidene complexes of metalloporphyrins (by depro-
tonation), the phosphinidene complexes possibly undergoing
phosphinidene transfer to alkenes or C-H bonds, analogous
to the carbene or imido transfer reactions of carbene8 and
imido metalloporphyrins,9 or (ii) metalloporphyrin complexes
bearing various tertiary phosphine ligands (by P-H bond
functionalization, which would be important either for
introducing functional groups to tertiary phosphine com-
plexes of metalloporphyrins or for tuning the electronic/steric
properties of these metal complexes). Furthermore, [M(Po-
r)(PH2R)2] and [M(Por)(PHR2)2] could be considered as a
unique type of the stabilized form of unstable PH2R or PHR2,
which have an intense unpleasant odor and are usually found
to be air-sensitive. Notable recent examples are [RuII(F20-
TPP)(PH2Ph)2] (F20-TPP ) 5,10,15,20-tetrakis(pentafluo-
rophenyl)porphyrinato dianion) and [RuII(F20-TPP)(PHPh2)2],
both exhibiting a remarkable stability in solutions open to
the air.7a Being located in close proximity to porphyrin
macrocycles, the coordinated P-H bonds could be func-
tionalized with a shape- or regioselectivity. A question is
whether the stabilized PH2R and PHR2 are active toward
P-H bond functionalization reactions.
We are interested in extending the chemistry of PH2R and
PHR2 complexes to iron porphyrins and to metallophthalo-
cyanines. Given the presence of iron porphyrin units in
hemoproteins, the binding behavior of PH2R or PHR2 toward
iron porphyrins would provide insight into the interaction
of hemoproteins with these types of phosphine substrates.
Metallophthalocyanines constitute a large family of metal
complexes that bear a close relationship with metallopor-
Results and Discussion
Synthesis. Reduction of [FeIII(Por)Cl] with Na2S2O4 fol-
lowed by treatment of the in situ formed iron(II) porphyrin
with excess PH2R or PHPh2 afforded [FeII(F20-TPP)(PH2R)2]
(R ) Ph, 1a; Ad, 1b) or [FeII(Por)(PHPh2)2] (Por ) F20-
TPP, 2a; 2,6-Cl2TPP, 2b) (2,6-Cl2TPP ) 5,10,15,20-tet-
rakis(2,6-dichlorophenyl)porphyrinato dianion) in about 60%
yields (Scheme 1).
The phthalocyanine complexes [RuII(Pc)(PH2Ph)2] (3a) and
[RuII(Pc)(PHPh2)2] (4) were prepared in 65% and 60% yields,
respectively, by the reaction of [RuII(Pc)(DMSO)2]11 with
PH2Ph or PHPh2 (Scheme 2). In a previous work, we
developed a one-pot synthesis of [RuII(Por)(PH2R)2] from
OdPCl2R or PCl2R.7b By extending this one-pot method to
(4) (a) Adachi, H.; Suzuki, H.; Miyazaki, Y.; Iimura, Y.; Hoshino, M.
Inorg. Chem. 2002, 41, 2518. (b) Stulz, E.; Sanders, J. K. M.; Montalti,
M.; Prodi, L.; Zaccheroni, N.; de Biani, F. F.; Grigiotti, E.; Zanello,
P. Inorg. Chem. 2002, 41, 5269. (c) Suzuki, H.; Miyazaki, Y.; Hoshino,
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Nakajima, K.; Iwayama, T. S.; Okimi, H.; Hoshino, M. Inorg. Chem.
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(5) (a) Stulz, E.; Ng, Y.-F.; Scott, S. M.; Sanders, J. K. M. Chem. Commun.
2002, 524. (b) Stulz, E.; Maue, M.; Feeder, N.; Teat, S. J.; Ng, Y.-F.;
Bond, A. D.; Darling, S. L.; Sanders, J. K. M. Inorg. Chem. 2002,
41, 5255. (c) Stulz, E.; Scott, S. M.; Bond, A. D.; Otto, S.; Sanders,
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J. Am. Chem. Soc. 1999, 121, 9120. (b) Leung, S. K.-Y.; Tsui, W.-
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Inorganic Chemistry, Vol. 47, No. 20, 2008 9167

Huang et al.
Scheme 1
Scheme 2
the phthalocyanine counterparts, we prepared [RuII(Pc)(PH2-
Ad)2] (3b) and [RuII(Pc)(PH2But)2] (3c) (both in 70% yield)
starting from OdPCl2Ad and PCl2But, respectively (Sch-
eme 2).
Attempts to isolate PH2R or PHR2 complexes of iron
phthalocyanine have not been successful. The reaction of
[Fe(Pc)] (purchased from Aldrich) with excess PH2Ph or
PHPh2 in tetrahydrofuran afforded an unstable product which
has not been clearly identified.
Compared with [RuII(Por)(PH2Ph)2] and [RuII(Por)(PH-
Ph2)2],7a the iron(II) counterparts 1 and 2 are much more air-
sensitive. When 5,10,15,20-tetrakis(p-R-phenyl)porphyrins (R
) H, TPP; Me, TTP; Cl, 4-Cl-TPP) were used, the correspond-
ing iron(II) complexes of PH2R or PHPh2 could not be isolated
in a pure form.
In contrast, the ruthenium(II) phthalocyanines 3 and 4 all
exhibit a remarkable stability toward air in both the solid
state and solution. The stability of [RuII(Pc)(PH2Ph)2] (3a)
and [RuII(Pc)(PHPh2)2] (4) is comparable to that of [RuII(F20-
TPP)(PH2Ph)2] and [RuII(F20-TPP)(PHPh2)2]; the latter com-
plexes bear a fluorinated porphyrin ligand and were found
to exhibit the highest stability among all previously reported
PH2R complexes of ruthenium porphyrins.7
Complexes 1-4 constitute new families of metal PH2R
and PHR2 complexes. From the literature, we have not found
other examples of primary or secondary phosphine com-
plexes of iron porphyrins and metallophthalocyanines, despite
the reports on a number of iron porphyrins12 and metalloph-
thalocyanines10 that bear tertiary phosphine axial ligands.
P-H Bond Functionalization. The P-H bonds of PH2R
and PHR2 can be functionalized in several ways, including
hydrophosphination with alkenes (or alkynes) and P-alky-
lation with haloalkanes. Isolated metal PH2R or PHR2
complexes that have been reported to undergo hydrophos-
phination13 or P-alkylation14 are sparse and are confined to
metal carbonyls. Both the hydrophosphination and P-alky-
9168 Inorganic Chemistry, Vol. 47, No. 20, 2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
Scheme 3
lation reactions require the use of bases, such as tBuLi, KH,
1,8-diazabicyclo[5.4.0]undec-7-ene, and Et3N, for the depro-
tonation of the coordinated PH2R or PHR2 to give the
corresponding phosphido complexes. Reactions of isolated
phosphido complexes of metal carbonyls with alkenes (or
alkynes) and haloalkanes (or other alkyl cation sources) to
afford hydrophosphination15 and P-alkylation16 products,
respectively, have been documented. Phosphido complexes
of platinum and ruthenium with di(tertiary phosphine)
auxiliary ligands instead of carbonyls are also known to
undergo hydrophosphination17a,b and P-alkylation.17c,d,18
Our efforts in functionalizing the P-H bonds coordinated
to metal complexes were initially focused on alkene hydro-
phosphination by [RuII(F20-TPP)(PH2Ph)2] and [RuII(F20-
Scheme 4
TPP)(PHPh2)2]. The iron(II) complexes 1 and 2 were not
employed in such studies due to their high air-sensitivity.
Treatment of [RuII(F20-TPP)(PH2Ph)2] with 4 equiv of
CH2dCHR (R ) CO2Et, CN) and tBuOK in acetone afforded
[RuII(F20-TPP)(P(CH2CH2R)2Ph)2] (R ) CO2Et, 5a; CN, 5b)
in ∼85% yields (Scheme 3). Similar reactions of [RuII(F20-
TPP)(PHPh2)2] with 2 equiv of CH2dCHR (R ) CO2Et, CN)
(12) (a) Spiro, T. G.; Burke, J. M. J. Am. Chem. Soc. 1976, 98, 5482. (b)
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t
and BuOK gave [RuII(F20-TPP)(P(CH2CH2R)Ph2)2] (R )
CO2Et, 6a; CN, 6b) in ∼80% yields (Scheme 3).
Upon isolation of the ruthenium(II) phthalocyanines 3a
and 4, which can be obtained from PH2Ph or PHPh2, RuCl3,
and inexpensive phthalonitrile, we examined their reactivity
toward P-H bond functionalization reactions.
t
Reaction of 3a with excess CH2dCHCN and BuOK in
tetrahydrofuran for 1 h resulted in the formation of
[RuII(Pc)(P(CH2CH2CN)2Ph)2] (7; Scheme 4), which was
isolated in 60% yield. When 3a was treated with MeI, instead
of CH2dCHCN, under similar conditions, the P-alkylation
(17) (a) Wicht, D. K.; Kourkine, I. V.; Lew, B. M.; Nthenge, J. M.; Glueck,
D. S. J. Am. Chem. Soc. 1997, 119, 5039. (b) Scriban, C.; Glueck,
D. S.; Zakharov, L. N.; Kassel, W. S.; DiPasquale, A. G.; Golen, J. A.;
Rheingold, A. L. Organometallics 2006, 25, 5757. (c) Scriban, C.;
Glueck, D. S. J. Am. Chem. Soc. 2006, 128, 2788. (d) Scriban, C.;
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26, 1788.
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Soc. 2006, 128, 2786.
Inorganic Chemistry, Vol. 47, No. 20, 2008 9169

Huang et al.
Scheme 5
n
product [RuII(Pc)(PMe2Ph)2] (8; Scheme 4) was obtained in
∼50% isolated yield.
could be extended to other haloalkanes such as BuBr and
BnCl (Bn ) benzyl), producing [RuII(Pc)(PRPh2)2] (R ) Bun,
10b; Bn, 10c; Scheme 6) in 50% and 62% yields, respectively.
We also examined the reactivity of 4 toward haloalkenes
and haloalkynes. Treatment of 4 with excess allylbromide
and tBuOK in tetrahydrofuran gave [RuII(Pc)(P(CH2-
CH)CH2)Ph2)2] (10d; Scheme 6) in 60% yield. No hydro-
phosphination of the alkene group in allylbromide was
observed. The reaction of 4 with excess MeCtCCH2Br and
tBuOK afforded [RuII(Pc)(P(CH2C≡CMe)Ph2)2] (10e; Scheme
6) in 58% yield. Replacing MeCtCCH2Br with propargyl-
bromide in the reaction led to the isolation of [RuII(Pc)(P-
(CHdCdCH2)Ph2)2] (10f; yield, 44%; Scheme 6), other than
[RuII(Pc)(P(CH2CtCH)Ph2)2]; analogous propargyl-allenyl
rearrangements have been reported in the literature.19
The reactions depicted in Schemes 4-6 demonstrate a
facile approach to ruthenium phthalocyanines bearing a
variety of tertiary phosphine axial ligands, of which, to the
best of our knowledge, the free sulfonyl phosphine
To examine the scope of the hydrophosphination and
P-alkylation of the P-H bonds coordinated to a metalloph-
thalocyanine, we focused the studies on complex 4 containing
a secondary arylphosphine ligand. When 4 was treated with
excess CH2dCHR (R ) CO2Et, CN) and tBuOK in tetrahy-
drofuran for 1 h, the reactions afforded [RuII(Pc)(P-
(CH2CH2R)Ph2)2] (R ) CO2Et, 9a; CN, 9b; Scheme 5) in
∼70% yields. Under similar conditions, 4 also reacted with
a series of other alkenes, including CH2dCHC(O)Me, CH2d
CHP(O)(OEt)2, CH2dCHS(O)2Ph, CH2dC(Me)CO2Me, and
CH(CO2Me)dCHCO2Me, to give the corresponding hydro-
phosphination products [RuII(Pc)(P(CH2CH2C(O)Me)Ph2)2]
(9c), [RuII(Pc)(P(CH2CH2P(O)(OEt)2)Ph2)2] (9d), [RuII-
(Pc)(P(CH2CH2S(O)2Ph)Ph2)2] (9e), [RuII(Pc)(P(CH2CH(Me)-
CO2Me)Ph2)2] (9f), and [RuII(Pc)(P(CH(CO2Me)CH2CO2-
Me)Ph2)2] (9g; Scheme 5) in 56-76% yields.
Replacement of the alkenes in the foregoing reactions of
4 by MeI resulted in the isolation of [RuII(Pc)(PMePh2)2]
(10a; Scheme 6) in 87% yield. This P-alkylation reaction
(19) Alcaide, B.; Almendros, P.; Aragoncillo, C.; Rodr´ıguez-Acebes, R.
Synthesis 2003, 1163.
9170 Inorganic Chemistry, Vol. 47, No. 20, 2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
Scheme 6
P(CH2CH2S(O)2Ph)Ph2 has not been reported previously, and
the P(CH2CH2C(O)Me)Ph2 and P(CH2CH(Me)CO2Me)Ph2
ligands have not been documented to bind metal ions. We
found that a direct reaction of [RuII(Pc)(DMSO)2] with excess
P(CH(CO2Me)CH2CO2Me)Ph2 in dichloromethane for 2 h
gave a mixture of products, from which 9g could not be
isolated in a pure form.
of these phenyl groups appear as a single set of three
signals (Hp, δ 6.63-6.94; Hm, δ 6.21-6.67; Ho, δ
4.11-4.68), except for 9g (see below).
1
At room temperature, the H and 31P NMR spectra of
[FeII(F20-TPP)(PH2R)2] (1a,b) in CDCl3 solution show broad
signals, unlike those of their ruthenium analogues.7 The 1H
NMR spectrum of 1a is depicted in Figure 1 as an example.
We suggest that there is a rapid exchange of PH2Ph between
its free and coordinated forms upon dissolving 1a in a CDCl3
solution. Indeed, lowering the temperature to -25 °C
markedly sharpens the NMR signals, resulting in the ap-
t
In the absence of BuOK, neither a hydrophosphination
nor a P-alkylation reaction was observed for the PH2Ph and
PHPh2 complexes of ruthenium(II) porphyrin and ruthe-
nium(II) phthalocyanine. This suggests that the P-H bond
functionalization reactions require in situ generation of the
corresponding phosphido complexes. Our attempts to isolate
the (PHPh)- or (PPh2)- complexes of a ruthenium porphyrin
or ruthenium phthalocyanine from the reaction of [RuII(F20-
TPP)(PH2Ph)2], [RuII(F20-TPP)(PHPh2)2], 3a, or 4 with
tBuOK have not been successful.
Spectral Features. i. NMR. Complexes 1-10 exhibit
diamagnetic NMR spectra, as expected for low-spin d6
iron(II) and ruthenium(II) complexes. The 1H NMR
spectra of the porphyrin complexes 1, 2, 5, and 6 show
pyrrolic proton resonances (Hꢀ) as a singlet in the δ range
of 8.09-8.60; the phthalocyanine complexes 3, 4, and
7-10 exhibit the proton resonances of the phthalocyanine
ligand as two multiplets at δ ∼9.0 and ∼7.9. The
phosphine ligands in 1-10, excluding 1b and 3b,c, each
bear at least one P-phenyl group; the proton resonances
1
pearance of a signal pattern (for both H and 31P NMR,
Figure 1) similar to that of [RuII(F20-TPP)(PH2Ph)2].7a This
indicates that, at low temperatures (<-25 °C), 1a undergoes
no significant phosphine dissociation in solution at an NMR
concentration (∼1 mM) and on the NMR time scale.
Compared with 1a,b, [FeII(F20-TPP)(PHPh2)2] (2a) is more
inert. In a CDCl3 solution of 2a at the NMR concentration
(∼1 mM), no significant dissociation of the coordinated
PHPh2 occurs at room temperature on the NMR time scale,
1
as revealed by its H and 31P NMR spectra that closely
resemble those of [RuII(F20-TPP)(PHPh2)2].7a Replacement
of the F20-TPP ligand in 2a with 2,6-Cl2TPP markedly
labilizes the complex in solution, since the 1H NMR spectrum
of 2b in the PH signal region is almost featureless at room
temperature, although such signals are well-resolved at
-25 °C.
Inorganic Chemistry, Vol. 47, No. 20, 2008 9171

Huang et al.
1
Figure 1. H NMR spectra of 1a in CDCl3 at +25 and -25 °C. Inset: 31P NMR spectrum of 1a in CDCl3 at -25 °C.
Ruthenium(II) phthalocyanines 3a-c and 4 all remain
tertiary phosphines. For P(CH2CH2R)2Ph (R ) CO2Et, CN)
complexes 5a,b, and 7, the two protons in each methylene
group (Ha,b or Hc,d) of the phosphine ligands are diaste-
reotopic and give different signals, as depicted in Figure S1
(see the Supporting Information) for 5b, which features a
set of four multiplets arising from Ha-d. In contrast, only
two multiplets were observed for the corresponding meth-
ylene protons in the P(CH2CH2R)Ph2 complexes 6a,b and
9a-e (see Figure S1 for 6b and Figure 3 for 9d), since the
two protons in each of these methylene group are equivalent.
The appearance of the methylene signals in the high-field
region is due to the ring current effect of the porphyrin or
phthalocyanine ligand.
intact in CDCl3 solutions at room temperature for at least
several days; their axial phosphine signals in the 1H and 31
P
NMR spectra are similar to those of the corresponding
complexes of ruthenium(II) porphyrins.7 Figure 2 depicts the
PH2 or PH signals in the 1H NMR spectra of 3a,c and 4 and
the 31P NMR spectra of the same complexes. Heating a
CDCl3 solution of 3a open to the air to 60 °C for 30 min
did not cause any appreciable change in its 1H and 31P NMR
spectra, revealing a remarkable stability of this primary
phosphine complex.
The room-temperature 1H NMR spectra of 5-10 in CDCl3
solutions reveal no detectable dissociation of the coordinated
9172 Inorganic Chemistry, Vol. 47, No. 20, 2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
1
Figure 2. H NMR spectra (in the P-H regions) and 31P NMR spectra of 3a,c and 4 in CDCl3. Some of the P-H signals of 3a,c overlap with the TMS
and But signals, respectively.
Complexes 9f and 9g have axial P(CH2CH(Me)CO2-
Me)Ph2 and P(CH(CO2Me)CH2CO2Me)Ph2 ligands, respec-
tively. Each of the tertiary diphenylphosphines has a
methylene group and a methine group; the two protons of
the methylene group are diastereotopic, and so are the two
phenyl groups. As a result, two well-separated sets of phenyl
signals, along with two multiplets from the methylene
whose signal appears at lower fields for 10d,e than for 10b.
In contrast, no P-methylene signal similar to that of 10e is
observed for 10f (Figure 4), which precludes formulation of
10f as a P(CH2CtCH)Ph2 complex.
The 31P{1H} NMR spectra of 1-10 show the phosphine
31P signal as a singlet, except for 9d (which gives the
corresponding signal as a triplet due to the presence of a
P(O)(OEt)2 group). For [MII(F20-TPP)(PH2Ph)2] with M )
Fe (1a) and Ru,7a the 31P signal appears at δ -34.8 and
-55.2, respectively, both at a lower field than that of
[RuII(Pc)(PH2Ph)2] (3a) with δ -57.2. This trend of chemical
shifts (Fe > Ru, F20-TPP > Pc) is parallel to those observed
for the secondary phosphine complexes [MII(F20-TPP)(PH-
1
protons, appear in the H NMR spectrum of 9g (Figure 3).
For 9f, the methylene proton resonances appear as two
multiplets, but there is only a single set of phenyl signals
(Figure 3), probably owing to longer distances of the phenyl
protons to the asymmetric methine C atom.
P-alkylation products 8 and 10a-c do not contain dias-
tereotopic methylene protons, like 6a,b and 9a-e. The R
signals of the PRPh2 ligands in 10b (R ) Bun), as compared
with those in 10d (R ) CH2CHdCH2), 10e (R )
CH2CtCMe), and 10f (R ) CHdCdCH2), are shown in
Figure 4. Complexes 10b,d,e each have a P-methylene group,
(20) Rawling, T.; McDonagh, A. Coord. Chem. ReV. 2007, 251, 1128.
(21) Ball, R. G.; Domazetis, G.; Dolphin, D.; James, B. R.; Trotter, J. Inorg.
Chem. 1981, 20, 1556.
Inorganic Chemistry, Vol. 47, No. 20, 2008 9173

Huang et al.
Figure 3. 1H NMR spectra of 9d,f,g in CDCl3 showing the signals of phthalocyanine (Pc) and the axial phosphine ligands except those of the OMe or OEt
groups.
Ph2)2] (M ) Fe (2a), δ 21.7; Ru, δ 9.97a) and [RuII-
(Pc)(PHPh2)2] (4, δ 3.7). The phosphine 31P chemical shifts
(δ) of 5-10 range from -1.3 to +16.2.
at 340-385 nm and 560-595 nm, in their UV-vis spectra.20
Similar UV-vis spectra were observed for 3, 4, and 7-10.
For 5 and 6, their UV-vis spectra show Soret and ꢀ bands
at 433-439 and 518-524 nm, respectively, which are typical
for tertiary phosphine complexes of ruthenium meso-tet-
raarylporphyins.21 The UV-vis spectra of 1 and 2 were
obtained under nitrogen in the presence of an excess of the
ii. UV-Vis Spectroscopy and Mass Spectrometry. Six-
coordinate ruthenium phthalocyanines are known to exhibit
an intense Soret band at 300-325 nm and an intense Q band
at 620-652 nm, together with two weaker shoulder bands
9174 Inorganic Chemistry, Vol. 47, No. 20, 2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
1
Figure 4. H NMR spectra of 10b,d,e,f in CDCl3 showing the signals of the axial phosphine ligands except those of the phenyl groups. The inset is an
enlargement of the Ha,b signal for 10f.
corresponding free PH2R or PHPh2, owing to the lability and
high air sensitivity of these complexes in solutions at room
temperature. The Soret bands (448-454 nm) and ꢀ bands
(546-552 nm) of 1 and 2 are comparable to those (Soret
450 nm, ꢀ 550 nm) of [FeII(TPP)(PPh3)2] (TPP ) 5,10,15,20-
tetraphenylporphyrinato dianion).12k
and [M-2L]+, where L is the corresponding phosphine
ligand in these complexes.
X-Ray Crystal Structural Determination. We have
obtained diffraction-quality crystals of 1a, 2b ·2CH2Cl2, 3b,c,
4, and 5b·2CH2Cl2 and determined their structures by X-ray
crystallography. The crystallographic data are compiled in
Tables 1 and 2, and the ORTEP drawings of the structures,
which all feature a planar porphyrin or phthalocyanine ring
In the mass spectra of 1-10, there are peaks that can be
assigned to the parent ions M+ and the fragments [M-L]+
Inorganic Chemistry, Vol. 47, No. 20, 2008 9175

Huang et al.
Table 1. Crystallographic Data of Porphyrin Complexes 1a,
2b·2CH2Cl2, and 5b·2CH2Cl2
Å). The P-C distance (1.844(5) Å) and Ru-P-C angle
(128.50(16)°) of [RuII(L)(PH2Ad)2] for L ) Pc (3b) are
almost identical to the corresponding values for L ) TTP
(P-C, 1.844(21) Å; Ru-P-C, 128.34(10)°).7b
1a
2b·2CH2Cl2
5b·2CH2Cl2
formula
cryst syst
fw
C56H22F20FeN4P2 C70H44Cl12FeN4P2 C72H42Cl8F20N8P2Ru
monoclinic
1248.57
triclinic
1484.28
j
monoclinic
1845.75
P21/c
Complex 5b has a Ru-P distance of 2.3754(10) Å, slightly
longer than that of 2.3603(10) Å in [RuII(F20-TPP)(PH2Ph)2]7a
but shorter than those in [RuII(TPP)(PPh2CH2PPh2)2] (2.398(3)
Å),21 [RuII(F20-TPP)(PPh3)2] (2.4643(9) Å),22 and [RuII(F28-
TPP)(PPh3)2] (2.4807(7) Å, F28-TPP ) 2,3,7,8,12,13,17,18-
octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)por-
phyrinato dianion).22 Likewise, the Fe-P distances in
[FeII(TPP)(PMe2Ph)2] (2.284(1) Å)12j and [FeII(TPP)(PBun3)2]
(2.3457(11) Å)12k are longer than that in the PH2Ph complex
1a. Considerably smaller M-P-C angles are found in the
tertiary phosphine complexes listed in Table 3 relative to
the PH2R or PHPh2 complexes 1a, 2b, 3b,c, and 4, regardless
of whether M ) Fe or Ru, and whether the auxiliary ligand
is porphyrin or phthalocyanine.
space group P21/c
P1
a, Å
b, Å
c, Å
R, deg
ꢀ, deg
γ, deg
V, Å3
Z
13.000(3)
12.279(4)
12.517(4)
12.727(4)
91.57(3)
107.00(3)
117.49(3)
1628.7(9)
1
13.205(3)
19.241(4)
15.281(3)
90.00
111.03(3)
90.00
3623.9(13)
2
1.691
7.7410(15)
25.641(5)
90.00
102.49(3)
90.00
2519.3(9)
2
F
calcd, g cm-3 1.646
2θ range, deg 51.28
1.513
55.14
1.08
51.28
1.13
GOF
1.03
R1/wR2
0.045/0.119
0.093/0.206
0.057/0.171
Table 2. Crystallographic Data of Phthalocyanine Complexes 3b, 3c,
and 4
3b
3c
4
Notably, in the crystal structures of the phthalocyanine
complexes 3c and 4, there are intermolecular C-H · · ·π
interactions, as depicted in Figure 6. Both 3c and 4 have
two independent types of molecules (A and B) in the
respective crystal structure, and the C-H · · · π interactions
(close H · · · C distances: 2.726-2.795 Å in 3c, 2.615-2.780
Å in 4) link each molecule A with four molecules B, and
vice versa. Such a linkage of molecules by C-H · · ·π
interactions generates a 3D network for 3c but 2D sheets
for 4; no significant C-H · · · π interactions are present
between the 2D sheets of the latter complex.
formula
cryst syst
fw
space group
a, Å
C52H46N8P2Ru
monoclinic
945.98
C40H60N8P2Ru
monoclinic
793.79
C56H38N8P2Ru
triclinic
985.95
j
P21/c
P21/c
P1
12.063(2)
12.717(2)
18.652(4)
90.00
92.15(3)°
90.00
2859.3(9)
2
1.099
51.32
0.98
17.976(4)
11.971(3
18.811(4)
90.00
111.83(3)
90.00
3757.7(15)
4
1.403
12.739(3)
12.791(3)
15.547(3)
107.99(3)
101.17(3)
97.94(3)
2310.0(8)
2
b, Å
c, Å
R, deg
ꢀ, deg
γ, deg
V, Å3
Z
F
calc, g cm-3
2θ range, deg
1.418
51.76
0.98
51.28
0.91
GOF
Conclusion
R1/wR2
0.069/0.187
0.061/0.169
0.035/0.084
and a crystallographic center of symmetry, are shown in
Figure 5. A comparison of the average geometrical param-
eters among these complexes and previously reported
iron(II)12j,k and ruthenium(II)7,21,22 porphyrin analogues is
given in Table 3.
We have isolated and characterized several primary and
secondary phosphine complexes of iron(II) porphyrins and
ruthenium(II) phthalocyanine, of which the iron complexes are
highly air-sensitive, but the ruthenium phthalocyanine com-
plexes are remarkably stable toward air in both the solid state
and solution. The PH2Ph and PHPh2 stabilized by ruthenium
phthalocyanine, and by ruthenium porphyrin F20-TPP as well,
can undergo hydrophosphination reactions with alkenes or
P-alkylation with halo compounds. Through such P-H bond
functionalization reactions, ruthenium phthalocyanine com-
plexes of a variety of tertiary phosphines bearing alkoxycar-
bonyl, cyano, ketyl, alkoxyphosphonyl, sulfonyl, alkene, alkyne,
and allene functional groups could be isolated.
For [MII(F20-TPP)(PH2Ph)2] (M ) Fe (1a), Ru7a), the M-P
distances (M ) Fe, 2.2597(9); Ru, 2.3603(10) Å), M-N
distances (M ) Fe, 1.998(2); Ru, 2.055(2) Å), P-C distances
(M ) Fe, 1.803(4); Ru, 1.824(3) Å), and M-P-C angles
(M ) Fe, 120.31(11)°; Ru, 129.11(11)°) follow an order of
Fe < Ru. A similar order was observed by comparing the
M-P and M-N distances of 2b (M ) Fe) with those of
[RuII(F20-TPP)(PHPh2)2]7a and [RuII(4-Cl-TPP)(PHPh2)2];7a
the former has a similar P-C distance and a slightly larger
M-P-C angle compared with the latter two ruthenium
analogues.
Experimental Section
General. All manipulations were performed under argon or
nitrogen by using standard Schlenk technique unless otherwise
specified. Dichloromethane and hexane were purified by a solvent
purification system (Innovative technology, Inc.). Tetrahydro-
furan (THF) and cyclohexane were distilled from CaH2; methanol
wasdistilledfrommagnesium/iodine.OdPCl2Ad,23 [RuII(F20-TPP)-
(PH2Ph)2],7a [RuII(F20-TPP)(PHPh2)2],7a and [RuII(Pc)(DM-
SO)2]11 were prepared by literature methods. Other reagents were
Prior to this work, no phosphine complex of a ruthenium
phthalocyanine has been structurally characterized by X-ray
crystallography, and the reported crystal structures of
ruthenium phthalocyanines are sparse.20 From the average
geometric parameters of [RuII(L)(PH2Ad)2] (L ) Pc (3b),
TTP7b) and [RuII(L)(PHPh2)2] (L ) Pc (4), 4-Cl-TPP,7a F20-
TPP7a), it is evident that the phthalocyanine complexes 3b
and 4 have comparable Ru-P distances (2.3478(11)-
2.3707(13) Å) and slightly shorter Ru-N distances (2.007(4)-
2.016(2) Å) relative to those of their porphyrin analogues
(Ru-P,2.3397(11)-2.3516(13)Å;Ru-N,2.050(3)-2.055(45)
(22) Che, C.-M.; Zhang, J.-L.; Zhang, R.; Huang, J.-S.; Lai, T.-S.; Tsui,
W.-M.; Zhou, X.-G.; Zhou, Z.-Y.; Zhu, N.; Chang, C. K. Chem.sEur.
J. 2005, 11, 7040.
(23) Stetter, H.; Last, W. D. Chem. Ber. 1969, 102, 3364.
9176 Inorganic Chemistry, Vol. 47, No. 20, 2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
Figure 5. ORTEP drawings for 1a, 2b, 3b,c, 4, and 5b with omission of the hydrogen atoms, except those bonded to P atoms (in 2b and 3b, the hydrogen
atoms bonded to P atoms were not located). Thermal ellipsoid probability level: 30%. For 3c and 4, there are two independent molecules in the unit cell;
only one molecule is shown.
purchased from Aldrich and were used as received. UV-vis
spectra were recorded on a Hewlett-Packard 8453 diode array
spectrophotometer (interfaced with an IBM-compatible PC). 1H
and 31P NMR spectra were recorded on a Bruker DPX-300, AV-
400, or DRX-500 spectrometer; the chemical shifts (δ, ppm)
are relative to tetramethylsilane (TMS) for H NMR and 85%
H3PO4 for 31P NMR. Fast atom bombardment (FAB) mass
spectra were recorded on a Finnigan MAT 95 mass spectrometer
with 3-nitrobenzyl alcohol as the matrix. Elemental analyses were
performed by the Institute of Chemistry, the Chinese Academy
of Sciences.
Preparation of [FeII(Por)(PH2R)2] and [FeII(Por)(PHR2)2]. A
solution of Na2S2O4 (100 mg) in water (5 mL) was mixed with
a solution of [FeIII(Por)Cl] (30 mg) in dichloromethane (15 mL)
under nitrogen. The mixture was stirred for 15 min, resulting in
a color change from dark red to bright red. Excess PH2Ph or
1
Inorganic Chemistry, Vol. 47, No. 20, 2008 9177

Huang et al.
Table 3. Average Values of M-P, M-N, and P-C Distances (Å) and M-P-C Angles (deg) for 1a, 2b (M ) Fe), 3b,c, 4, and 5b (M ) Ru) as
Compared with Those for the Previously Reported Iron(II) and Ruthenium(II) Porphyrin Analogues
complex
M-P
M-N
P-C
M-P-C
[FeII(F20-TPP)(PH2Ph)2] (1a)
[FeII(2,6-Cl2TPP)(PHPh2)2] (2b)
[RuII(Pc)(PH2Ad)2] (3b)
[RuII(Pc)(PH2But)2] (3c)
[RuII(Pc)(PHPh2)2] (4)
2.2597(9)
2.309(2)
2.3707(13)
2.373(2)
2.3478(11)
2.3603(10)
2.358(20)
2.349(26)
2.3516(13)
2.3397(11)
2.3754(10)
2.284(1)
1.998(2)
1.999(5)
2.007(4)
2.002(4)
2.016(2)
2.055(2)
2.052(25)
2.055(45)
2.055(3)
2.050(3)
2.057(3)
2.000(1)
1.996(3)
2.042(8)
2.046(3)
2.0497(18)
1.803(4)
1.817(7)
1.844(5)
1.758(9)
1.844(4)
1.824(3)
1.811(18)
1.844(21)
1.817(4)
1.814(4)
1.834(5)
1.819(2)
1.839(6)
1.83(1)
120.31(11)
123.1(2)
128.50(16)
133.6(4)
120.33(12)
129.11(11)
120.41(11)
128.34(10)
121.17(12)
119.72(14)
113.85(15)
115.97(9)
115.76(15)
115.7(4)
[RuII(F20-TPP)(PH2Ph)2]7a
[RuII(F20-TPP)(PH2Mes)2]7b
7b
[RuII(TTP)(PH2Ad)2]·2C5H12
[RuII(F20-TPP)(PHPh2)2]7a
[RuII(4-Cl-TPP)(PHPh2)2]7a
[RuII(F20-TPP)(P(CH2CH2CN)2Ph)2] (5b)
[FeII(TPP)(PMe2Ph)2]12j
[FeII(TPP)(PBun )2]12k
2.3457(11)
2.398(3)
2.4643(9)
2.4807(7)
3
[RuII(TPP)(PPh2CH2PPh2)2]21
[RuII(F20-TPP)(PPh3)2]22
[RuII(F28-TPP)(PPh3)2]22
1.850(3)
1.839(3)
116.54(11)
115.95(9)
PHPh2 (neat liquid, two drops) or PH2Ad (4 equiv) was then
added. Upon stirring for 5 min, the organic phase was separated
from the aqueous one, dried with anhydrous Na2SO4, and
evaporated to dryness in vacuo. The crude product (dark red
solid) was purified by washing with hexane.
[FeII(F20-TPP)(PH2Ph)2] (1a). Yield: 56%. 1H NMR (400 MHz,
CDCl3, -25 °C): δ Hꢀ 8.34 (s, 8H); Hp 6.65 (m, 2H); Hm 6.29 (m,
4H); Ho 4.16 (m, 4H); PH2 -0.39 (s), -0.46 (s), -0.59 (br), -0.82
(br), -0.94 (s), -1.02 (s) (a total of 4H). 31P{1H} NMR (162 Hz,
CDCl3, -25 °C): δ -34.8. UV-vis (CH2Cl2 containing 2 × 10-2
M of PH2Ph): λmax 415 sh, 448 (Soret), 546 nm. FAB MS: m/z
1248 (M+), 1138 ([M - PH2Ph]+), 1028 ([M - 2PH2Ph]+). Anal.
calcd for C56H22F20FeN4P2: C, 53.87; H, 1.78; N, 4.49. Found: C,
54.11; H, 1.90; N, 4.34.
[FeII(F20-TPP)(PH2Ad)2] (1b). Yield: 64%. 1H NMR (500 MHz,
CDCl3, -25 °C): δ Hꢀ 8.38 (s, 8H); Ad 0.83 (s, 12H), 0.54 (m,
6H), -1.31 (s, 12H); PH2 -1.98 (s), -2.10 (s), -2.21 (br), -2.50
(br), -2.62 (s), -2.74 (s) (a total of 4H). 31P{1H} NMR (162 MHz,
CDCl3, -25 °C): δ -8.7. UV-vis (CH2Cl2 containing 2 × 10-2
M of PH2Ad): λmax 410 sh, 451 (Soret), 551 nm. FAB MS: m/z
1364 (M+), 1196 ([M - PH2Ad]+), 1028 ([M - 2PH2Ad]+). Anal.
calcd for C64H42F20FeN4P2: C, 56.32; H, 3.10; N, 4.11. Found: C,
56.68; H, 2.94; N, 3.88.
formation of a dark blue-purple precipitate. The precipitate was
collected by filtration and washed with hexane until the filtrate
became colorless.
[RuII(Pc)(PH2Ph)2] (3a). Yield: 65%. 1H NMR (400 MHz,
CDCl3): δ Pc 9.11 (m, 8H), 7.91 (m, 8H); Hp 6.65 (m, 2H); Hm
6.23 (m, 4H); Ho 4.32 (m, 4H); PH2 0.17 (s), 0.03 (br) -0.13 (br),
-0.37 (br), -0.53 (s), -0.67 (s) ppm (a total of 4H). 31P{1H} NMR
(162 MHz, CDCl3): δ -57.2. UV-vis (1.3 × 10-5 M, CH2Cl2):
λmax (log ε) 315 (4.8), 402 (3.9) sh, 582 (4.3) sh, 640 (4.8) nm.
FAB MS: m/z 834 (M+), 724 ([M - PH2Ph]+), 614 ([M -
2PH2Ph]+). Anal. calcd for C44H30N8P2Ru ·CH2Cl2: C, 58.83; H,
3.51; N, 12.20. Found: C, 58.82; H, 3.51; N, 12.42.
[RuII(Pc)(PHPh2)2] (4). Yield: 60%. 1H NMR (400 MHz,
CDCl3): δ Pc 9.03 (m, 8H), 7.87 (m, 8H); Hp 6.63 (m, 4H); Hm
6.24 (m, 8H); Ho 4.43 (m, 8H); PH 0.80 (s), 0.51 (br), 0.23 (br),
-0.05 (s) (a total of 2H). 31P{1H} NMR (162 MHz, CDCl3): δ
3.7. UV-vis (1.4 × 10-5 M, CH2Cl2): λmax (log ε) 291 (4.8), 410
(4.0) sh, 580 (4.3) sh, 640 (4.8) nm. FAB MS: m/z 986 (M+), 800
([M - PHPh2]+), 614 ([M - 2PHPh2]+). Anal. calcd for
C56H38N8P2Ru · CH2Cl2: C, 63.93; H, 3.76; N, 10.46. Found: C,
64.07; H, 3.85; N, 10.57.
Preparation of [RuII(Pc)(PH2R)2] (R ) Ad, 3b; But, 3c).
LiAlH4 (500 mg) was added to a mixture of [RuII(Pc)(DMSO)2]
(500 mg, 0.65 mmol) and OdPCl2Ad (658 mg, 2.6 mmol, for 3b)
or PCl2But (413 mg, 2.6 mmol, for 3c) in dichloromethane. The
mixture was stirred overnight and subsequently treated with
methanol until no H2 bubbles evolved. After filtration, the filtrate
was evaporated to dryness to give a dark blue-purple solid. The
solid was collected, washed with methanol, and recrystallized from
dichloromethane-hexane.
[FeII(F20-TPP)(PHPh2)2] (2a). Yield: 60%. 1H NMR (400 MHz,
CDCl3): δ Hꢀ 8.25 (s, 8H); Hp 6.71 (m, 4H); Hm 6.38 (m, 8H); Ho
4.35 (m, 8H); PH 0.35 (s), 0.10 (br), -0.24 (br), -0.49 (s) (a total
of 2H). 31P{1H} NMR (162 MHz, CDCl3): δ 21.7. UV-vis (CH2Cl2
containing 2 × 10-2 M of PHPh2): λmax 454 (Soret), 550 nm. FAB
MS: m/z 1401 ([M + H]+), 1214 ([M - PHPh2]+), 1028 ([M -
2PHPh2]+). Anal. calcd for C68H30F20FeN4P2: C, 58.31; H, 2.16;
N, 4.00. Found: C, 58.68; H, 2.28; N, 3.84.
[RuII(Pc)(PH2Ad)2] (3b). Yield: 70%. 1H NMR (400 MHz,
CDCl3): δ Pc 9.22 (m, 8H), 7.94 (m, 8H); Ad 0.86 (m, 12H), 0.44
(m, 6H), -1.14 (s, 12H); PH2 -1.38 (s), -1.50 (s), -1.66 (br),
-1.90 (br), -2.05 (s), -2.17 (s) (a total of 4H). 31P{1H} NMR
(162 MHz, CDCl3): δ -23.4. UV-vis (1.1 × 10-5 M, CH2Cl2):
λmax (log ε) 316 (4.8), 403 (3.9) sh, 578 (4.3) sh, 637 (4.8). FAB
MS: m/z 950 (M+), 782 ([M - PH2Ad]+), 614 ([M - 2PH2Ad]+).
Anal. calcd for C52H50N8P2Ru·CH2Cl2: C, 61.51; H, 5.06; N, 10.83.
Found: C, 61.71; H, 4.94; N, 11.02.
[RuII(Pc)(PH2But)2] (3c). Yield: 70%. 1H NMR (300 MHz,
CDCl3): δ Pc 9.23 (m, 8H), 7.96 (m, 8H); But and PH2 -1.28 (m,
19H), -1.02 (s), -1.70 (br), -1.91 (br), -2.07 (s) (a total of 3H).
31P{1H} NMR (162 MHz, CDCl3): δ -18.2. UV-vis (1.8 × 10-5
M, CH2Cl2): λmax (log ε) 316 (4.4), 403 (3.4) sh, 579 (3.8) sh, 638
(4.4). FAB MS: m/z 794 (M+), 704 ([M - PH2But]+), 614 ([M -
1
[FeII(2,6-Cl2TPP)(PHPh2)2] (2b). Yield: 61%. H NMR (500
MHz, CDCl3, -25 °C): δ Hꢀ 8.28 (s, 8H); H′m 7.62 (m, 8H); H′p
7.53 (m, 4H); Hp 6.58 (m, 4H); Hm 6.31 (m, 8H); Ho 4.68 (m, 8H);
PH 0.67 (s), 0.47 (br), 0.18 (br), -0.02 (s) (a total of 2H). (H′m
and H′p are the phenyl signals of the 2,6-Cl2TPP ligand). 31P{1H}
NMR (202 MHz, CDCl3, -25 °C): δ 21.0. UV-vis (CH2Cl2
containing 2 × 10-2 M of PHPh2): λmax 454 (Soret), 552 nm. FAB
MS: m/z 1316 (M+), 1130 ([M - PHPh2]+), 944 ([M - 2PHPh2]+).
Anal. calcd for C68H42Cl8FeN4P2 ·H2O: C, 61.20; H, 3.32; N, 4.20.
Found: C, 61.52; H, 3.46; N, 4.00.
Preparation of [RuII(Pc)(PH2Ph)2] and [RuII(Pc)(PHPh2)2].
Phenylphosphine or diphenylphosphine (10 wt % in hexane, 10
mL) was added to a solution of [RuII(Pc)(DMSO)2] (500 mg, 0.65
mmol) in dichloromethane (20 mL). The mixture was stirred
overnight and then treated with hexane (50 mL), leading to the
9178 Inorganic Chemistry, Vol. 47, No. 20, 2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
Figure 6. C-H· · ·π interactions in the crystal structures of 3c and 4. For 4, the PHPh2 phenyl groups not involved in the C-H· · ·π interactions are not
shown, except for their C atoms bonded to the P atoms.
2PH2But]+). Anal. calcd for C40H38N8P2Ru·CH2Cl2 ·H2O: C, 54.91;
H, 4.72; N, 12.49. Found: C, 54.89; H, 4.70; N, 12.36.
(4.4 mg, 0.04 mmol). The color of the solution changed from red
to red-brown immediately. The mixture was stirred for 10 min and
then evaporated in vacuo to a volume of 1 mL. The addition of
diethyl ether (10 mL) led to the precipitation of 5 or 6 as a red-
purple solid, which was collected by filtration, washed with three
portions of diethyl ether (3 × 5 mL), and dried in vacuo.
Reaction of [RuII(F20-TPP)(PH2Ph)2] or [RuII(F20-TPP)(PH-
Ph2)2] with Alkenes CH2dCHR (R ) CO2Et, CN) and Isola-
tion of [RuII(F20-TPP)(P(CH2CH2R)2Ph)2] (5) or [RuII(F20-
TPP)(P(CH2CH2R)Ph2)2] (6). [RuII(F20-TPP)(PH2Ph)2] or [RuII(F20-
TPP)(PHPh2)2] (0.01 mmol) was dissolved in acetone (20 mL)
and then degassed for 5 min. To this solution was added
CH2dCHCO2Et or CH2dCHCN (0.04 mmol for [RuII(F20-
TPP)(PH2Ph)2], 0.02 mmol for [RuII(F20-TPP)(PHPh2)2]) and tBuOK
1
[RuII(F20-TPP)(P(CH2CH2CO2Et)2Ph)2] (5a). Yield: 85%. H
NMR (300 MHz, CDCl3): δ Hꢀ 8.14 (s, 8H); Hp 6.75 (m, 2H); Hm
6.50 (m, 4H); Ho 4.39 (m, 4H); Et 3.75 (m, 8H), 0.99 (t, J ) 6.5 Hz,
12 H); Hc, Hd -0.04 (m, 4H), -0.18 (m, 4H); Ha, Hb -1.44 (m, 4H),
Inorganic Chemistry, Vol. 47, No. 20, 2008 9179

Huang et al.
-1.98 (m, 4H). 31P{1H} NMR (400 MHz, CDCl3): δ 8.1. UV-vis
(CH2Cl2): λmax 419 sh, 439 (Soret), 524 nm. FAB MS: m/z 1695 ([M
+ H]+), 1384 ([M - P(CH2CH2CO2Et)2Ph]+), 1074 ([M -
2P(CH2CH2CO2Et)2Ph]+). Anal. calcd for C76H54F20N4O8P2Ru: C,
53.88; H, 3.21; N, 3.31. Found: C, 54.31; H, 3.40; N, 3.48.
[RuII(F20-TPP)(P(CH2CH2CN)2Ph)2] (5b). Yield: 87%. 1H
NMR (400 MHz, (CD3)2CO): δ Hꢀ 8.60 (s, 8H); Hp 6.94 (m, 2H);
Hm 6.67 (m, 4H); Ho 4.43 (m, 4H); Hc, Hd 0.23 (m, 4H), 0.06 (m,
4H); Ha, Hb -1.34 (m, 4H), -1.83 (m, 4H). 31P{1H} NMR (400
MHz, (CD3)2CO): δ 8.3 ppm. UV-vis (CH2Cl2): λmax 413 sh, 433
(Soret), 518 nm. FAB MS: m/z 1507 ([M + H]+), 1290 ([M -
P(CH2CH2CN)2Ph]+), 1074 ([M - 2P(CH2CH2CN)2Ph]+). Anal.
calcd for C68H34F20N8P2Ru: C, 54.23; H, 2.28; N, 7.44. Found: C,
53.91; H, 2.43; N, 7.62.
10-5 M, CH2Cl2): λmax (log ε) 297 (4.3), 418 (3.4) sh, 581 (3.8) sh,
639 (4.2) nm. FAB MS: m/z 1186 (M+), 900 ([M
-
P(CH2CH2CO2Et)Ph2]+), 614 ([M - 2P(CH2CH2CO2Et)Ph2]+).
Anal. calcd for C66H54N8O4P2Ru·CH2Cl2: C, 63.31; H, 4.44; N,
8.82. Found: C, 63.04; H, 4.32; N, 8.84.
[RuII(Pc)(P(CH2CH2CN)Ph2)2] (9b). Yield: 74%. 1H NMR (300
MHz, CDCl3): δ Pc 9.03 (m, 8H), 7.91 (m, 8H); Hp 6.78 (m, 4H);
Hm 6.35 (m, 8H); Ho 4.37 (m, 8H); Hb -0.20 (m, 4H); Ha -1.56
(m, 4H). 31P{1H} NMR (162 MHz, CDCl3): δ 10.3. UV-vis (1.1
× 10-5 M, CH2Cl2): λmax (log ε) 296 (4.6), 418 (3.5) sh, 582 (4.1)
sh, 641 (4.5) nm. FAB MS: m/z 1092 (M+), 853 ([M -
P(CH2CH2CN)Ph2]+), 614 ([M - 2P(CH2CH2CN)Ph2]+). Anal.
calcd for C62H44N10P2Ru·2CH2Cl2: C, 60.91; H, 3.83; N, 11.10.
Found: C, 61.09; H, 4.00; N, 10.95.
[RuII(F20-TPP)(P(CH2CH2CO2Et)Ph2)2] (6a). Yield: 80%. 1H
NMR (300 MHz, CD3Cl): δ Hꢀ 8.09 (s, 8H); Hp 6.77 (m, 4H); Hm
6.49 (m, 8H); Ho 4.33 (m, 8H); Et 3.63 (q, J ) 7.1 Hz, 4H), 0.92
(t, J ) 7.1 Hz, 6H); Hb -0.25 (m, 4H); Ha -1.71 (m, 4H). 31P{1H}
NMR (400 MHz, (CD3)2CO): δ 9.9. UV-vis (CH2Cl2): λmax 421
sh, 439 (Soret), 524 nm. FAB MS: m/z 1647 ([M + H]+), 1360
([M -P(CH2CH2CO2Et)Ph2]+), 1074 ([M -2P(CH2CH2CO2Et)Ph2]+).
Anal. calcd for C78H46F20N4O4P2Ru: C, 56.91; H, 2.82; N, 3.40.
Found: C, 56.81; H, 2.97; N, 3.18.
[RuII(F20-TPP)(P(CH2CH2CN)Ph2)2] (6b). Yield: 82%. 1H
NMR (400 MHz, (CD3)2CO): δ Hꢀ 8.42 (s, 8H); Hp 6.87 (m, 4H);
Hm 6.57 (m, 8H); Ho 4.34 (m, 8H); Hb -0.25 (m, 4H); Ha -1.66
(m, 4H). 31P{1H} NMR (400 MHz, (CD3)2CO): δ 9.6. UV-vis
(CH2Cl2): λmax 412 sh, 438 (Soret), 520 nm. FAB MS: m/z 1553
([M + H]+), 1313 ([M - P(CH2CH2CN)Ph2]+), 1074 ([M -
2P(CH2CH2CN)Ph2]+). Anal. calcd for C74H36F20N6P2Ru·H2O: C,
56.61; H, 2.44; N, 5.35. Found: C, 56.24; H, 2.41; N, 5.19.
Reaction of [RuII(Pc)(PH2Ph)2] or [RuII(Pc)(PHPh2)2] with
Alkenes CH(R1)dCR2R3 (R1 ) R2 ) H, R3 ) CO2Et, CN,
C(O)Me, P(O)(OEt)2, S(O)2Ph; R1 ) H, R2 ) Me, R3 ) CO2Me;
R1 ) R3 ) CO2Me, R2 ) H) and Isolation of [RuII(Pc)(P(CH2-
CH2CN)2Ph)2] (7) or [RuII(Pc)(P(CH(R1)CHR2R3)Ph2)2] (9). To a
solution of [RuII(Pc)(PH2Ph)2] or [RuII(Pc)(PHPh2)2] (40 mg) in
THF (6 mL) was added CH(R1)dCR2R3 (20 mg for the alkene
with R1 ) R2 ) H, R3 ) S(O)2Ph; 20 µL for the other alkenes)
and tBuOK (20 mg). The mixture was stirred for 1 h, followed by
removal of the solvent in vacuo. The residue was dissolved in
dichloromethane. Upon filtration, the filtrate was evaporated in
vacuo to dryness, and the residual dark blue-purple solid was
recrystallized from dichloromethane-cyclohexane.
[RuII(Pc)(P(CH2CH2C(O)Me)Ph2)2] (9c). Yield: 66%. 1H NMR
(300 MHz, CDCl3): δ Pc 9.01 (m, 8H), 7.87 (m, 8H); Hp 6.73 (m,
4H); Hm 6.30 (m, 8H); Ho 4.40 (m, 8H); Me 1.05 (s, 6H); Hb -0.29
(m, 4H); Ha -1.41 (m, 4H). 31P{1H} NMR (162 MHz, CDCl3): δ
8.3. UV-vis (1.5 × 10-5 M, CH2Cl2): λmax (log ε) 296 (4.6), 419
(3.6) sh, 578 (4.1) sh, 638 (4.5) nm. FAB MS: m/z 1126 (M+),
870 ([M - P(CH2CH2C(O)Me)Ph2]+), 614 ([M - 2P(CH2CH2C-
(O)Me)Ph2]+). Anal. calcd for C64H50N8O2P2Ru·2CH2Cl2: C, 61.16;
H, 4.20; N, 8.65. Found: C, 60.85; H, 4.24; N, 8.65.
1
[RuII(Pc)(P(CH2CH2P(O)(OEt)2)Ph2)2] (9d). Yield: 63%. H
NMR (300 MHz, CDCl3): δ Pc 8.99 (m, 8H), 7.85 (m, 8H); Hp
6.74 (m, 4H); Hm 6.34 (m, 8H); Ho 4.39 (m, 8H); Et 3.45 (m, 8H),
0.96 (m, 12H); Hb -0.77 (m, 4H); Ha -1.74 (m, 4H). 31P{1H}
NMR (162 MHz, CDCl3): δ 29.4 (t), 14.3 (t). UV-vis (8.3 × 10-5
M, CH2Cl2): λmax (log ε) 298 (4.4), 418 (3.7) sh, 582 (4.2) sh, 637
(4.4) nm. FAB MS: m/z 1314 (M+), 964 ([M - P(CH2-
CH2P(O)(OEt)2)Ph2]+), 614 ([M - 2P(CH2CH2P(O)(OEt)2)Ph2]+).
Anal. calcd for C68H64N8O6P4Ru·CH2Cl2: C, 59.23; H, 4.75; N,
8.01. Found: C, 59.39; H, 4.72; N, 8.23.
[RuII(Pc)(P(CH2CH2S(O)2Ph)Ph2)2] (9e). Yield: 76%. 1H NMR
(300 MHz, CDCl3): δ Pc 9.00 (m, 8H), 7.91 (m, 8H); S(O)2Ph
7.60 (m, 4H), 7.31 (m, 2H), 6.96 (m, 4H); Hp 6.69 (m, 4H); Hm
6.21 (m, 8H); Ho 4.11 (m, 8H); Hb 0.52 (m, 4H); Ha -1.77 (m,
4H). 31P{1H} NMR (162 MHz, CDCl3): δ 11.1. UV-vis (3.0 ×
10-5 M, CH2Cl2): λmax (log ε) 295 (4.4), 418 (3.4) sh, 580 (3.8) sh,
641 (4.3) nm. FAB MS: m/z 1322 (M+), 968 ([M
-
P(CH2CH2S(O)2Ph)Ph2]+), 614 ([M - 2P(CH2CH2S(O)2Ph)Ph2]+).
Anal. calcd for C72H54N8O4P2S2Ru·3CH2Cl2: C, 57.11; H, 3.83;
N, 7.10. Found: C, 57.48; H, 4.05; N, 6.90.
[RuII(Pc)(P(CH2CH(Me)CO2Me)Ph2)2] (9f). Yield: 56%. H
1
[RuII(Pc)(P(CH2CH2CN)2Ph)2] (7). Yield: 60%. 1H NMR (300
MHz, CDCl3): δ Pc 9.10 (m, 8H), 7.98 (m, 8H); Hp 6.84 (m, 2H);
Hm 6.40 (m, 4H); Ho 4.24 (m, 4H); Hc, Hd 0.16 (m, 4H), -0.02
(m, 4H); Ha, Hb -1.21 (m, 4H), -1.71 (m, 4H). 31P{1H} NMR
(162 MHz, CDCl3): δ 11.0. UV-vis (5.5 × 10-5 M, CH2Cl2): λmax
(log ε) 315 (4.4), 438 (3.3) sh, 581 (3.9) sh, 640 (4.3) nm. FAB
MS: m/z 1046 (M+), 830 ([M - P(CH2CH2CN)2Ph]+), 614 ([M -
2P(CH2CH2CN)2Ph]+). Anal. calcd for C56H42N12P2Ru·CH2Cl2: C,
60.53; H, 3.92; N, 14.86. Found: C, 60.58; H, 3.99; N, 14.98.
[RuII(Pc)(P(CH2CH2CO2Et)Ph2)2] (9a). Yield: 68%. 1H NMR
(300 MHz, CDCl3): δ Pc 9.01 (m, 8H), 7.85 (m, 8H); Hp 6.71 (m,
4H); Hm 6.29 (m, 8H); Ho 4.40 (m, 8H); Et 3.46 (q, J ) 6.5 Hz,
4H), 0.81 (t, J ) 6.1 Hz, 6H); Hb -0.22 (m, 4H); Ha -1.51 (m,
4H). 31P{1H} NMR (202 MHz, CDCl3): δ 10.5. UV-vis (7.8 ×
NMR (300 MHz, CDCl3): δ Pc 9.00 (m, 8H), 7.85 (m, 8H); Hp
6.70 (m, 4H); Hm 6.25 (m, 8H); Ho 4.40 (m, 8H); Me′ 2.46 (s,
6H); Hc -0.04 (br, 2H); Me -0.31 (m, 6H); Ha, Hb -1.08 (m,
2H), -2.02 (m, 2H). 31P{1H} NMR (162 MHz, CDCl3): δ 10.6.
UV-vis (7.3 × 10-5 M, CH2Cl2): λmax (log ε) 302 (4.5), 418 (3.8)
sh, 582 (4.3) sh, 637 (4.6) nm. FAB MS: m/z 1186 (M+), 900 ([M
- P(CH2CH(Me)CO2Me)Ph2]+), 614 ([M - 2P(CH2CH(Me)-
CO2Me)Ph2]+). Anal. calcd for C66H54N8O4P2Ru ·CH2Cl2: C, 63.31;
H, 4.44; N, 8.82. Found: C, 63.27; H, 4.18; N, 8.74.
[RuII(Pc)(P(CH(CO2Me)CH2CO2Me)Ph2)2] (9g). Yield: 72%.
1H NMR (300 MHz, CDCl3): δ Pc 9.00 (m, 8H), 7.89 (m, 8H); Hp
6.95 (m, 2H), 6.67 (m, 2H); Hm 6.27 (m, 4H), 6.17(m, 4H); Ho
4.63 (m, 4H), 4.35 (m, 4H); Me 3.06 (m, 6H), 2.50 (s, 6H); Hb, Hc
-0.28 (m, 2H), -0.40 (m, 2H); Ha -1.05 (br, 2H). (The multiplet
at δ 3.06 became a singlet upon raising the temperature to 60 °C.)
31P{1H} NMR (162 MHz, CDCl3): δ 9.1. UV-vis (1.4 × 10-5 M,
CH2Cl2): λmax (log ε) 299 (4.7), 416 (3.7) sh, 581 (4.3) sh, 643
(4.7) nm. FAB MS: m/z 1274 (M+), 944 ([M - P(CH-
(CO2Me)CH2CO2Me)Ph2]+), 614 ([M - 2P(CH(CO2Me)CH2-
(24) Otwinowski, Z.; Minor, W. In Methods in Enzymology; Carter, C. W.,
Jr., Sweet, R. M., Eds.; Academic Press: New York, 1997; Vol. 276:
Macromolecular Crystallography, Part A, p 307.
(25) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.;
Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.;
Spagna, R. J. Appl. Crystallogr. 1999, 32, 115.
9180 Inorganic Chemistry, Vol. 47, No. 20, 2008

Phosphine Complexes of Fe Porphyrins and Ru Phthalocyanine
CO2Me)Ph2]+). Anal. calcd for C68H54N8O8P2Ru · 1.5CH2Cl2: C,
59.56; H, 4.10; N, 7.99. Found: C, 59.36; H, 4.43; N, 7.60.
Reaction of [RuII(Pc)(PH2Ph)2] or [RuII(Pc)(PHPh2)2] with
RX (X ) I, R ) Me; X ) Br, R ) Bun, CH2dCHCH2,
MeCtCCH2, HCtCCH2; X ) Cl, R ) Bn) and Isolation of
[RuII(Pc)(PMe2Ph)2] (8) or [RuII(Pc)(PRPh2)2] (10). The proce-
dure is similar to that for the reaction of [RuII(Pc)(PH2Ph)2] or
[RuII(Pc)(PHPh2)2] with alkenes CH(R1)dCR2R3, except that halo
compounds RX (20 µL), instead of alkenes, were used.
4H); Hm 6.27 (m, 8H); Ho 4.65 (m, 8H); Ha, Hb 1.27 (m, 6H). 31P{1H}
NMR (162 MHz, CDCl3): δ -0.8. UV-vis (1.4 × 10-5 M, CH2Cl2):
λ
max (log ε) 299 (4.6), 415 (3.7) sh, 578 (4.0) sh, 642 (4.5) nm. FAB
MS: m/z 1062 (M+), 838 ([M - P(CHdCdCH2)Ph2]+), 614 ([M -
2P(CHdCdCH2)Ph2]+). Anal. calcd for C62H42N8P2Ru·CH2Cl2: C,
65.97; H, 3.87; N, 9.77. Found: C, 66.29; H, 3.72; N, 10.05.
X-Ray Crystal Structure Determinations of 1a, 2b ·2CH2Cl2,
3b,c, 4, and 5b ·2CH2Cl2. Diffraction-quality crystals were obtained
by the slow evaporation of dichloromethane/hexane solutions at room
temperature under argon for 1a (0.35 × 0.3 × 0.25 mm3) and
2b·2CH2Cl2 (0.5 × 0.3 × 0.25 mm3), by the same method, except
that the solution was open to air, for 5b·2CH2Cl2 (0.3 × 0.3 × 0.25
mm3), and by layering pentane on the top of chloroform solutions for
3b (0.6 × 0.4 × 0.15 mm3), 3c (0.6 × 0.25 × 0.15 mm3), and 4 (0.4
× 0.3 × 0.25 mm3). Each crystal was mounted in a glass capillary.
The data were collected at 28 °C using graphite monochromatized
Mo KR radiation (λ ) 0.71073 Å) on a MAR diffractometer with a
300 mm image plate detector (oscillation step of ꢁ, 1.5° for 3b,c and
2° for 1a, 4, 5b·2CH2Cl2; exposure time, 5 min for 4 and 10 min for
1a, 3b,c, 5b·2CH2Cl2; scanner distance, 120 mm; images collected,
90 for 5b·2CH2Cl2, 100 for 1a and 4, 130 for 3b,c; the images were
interpreted and the intensities were integrated using program DEN-
ZO24), except for 2b·2CH2Cl2, the data of which were collected on a
Bruker Smart CCD 1000 diffractometer. The structures were solved
by direct methods using the SIR-97 program25 (1a, 2b·2CH2Cl2, 3b,c,
and 5b·2CH2Cl2) or SHELXS-97 program26 (4) on a PC. Many non-H
atoms (including P and Fe or Ru) were located according to direct
methods and the successive least-squares Fourier cycles. Positions of
other non-hydrogen atoms were found after successful refinement by
full-matrix least-squares using the SHELXL-97 program27 on a PC.
There is half of a formula unit in the asymmetric unit for 1a,
2b·2CH2Cl2, 3b, and 5b·2CH2Cl2, whereas the asymmetric unit for
3c and 4 contains a half of each of the two independent molecules.
The H atoms on P in 1a and 4 were added according to the difference
Fourier map and refined isotropically; those in 3c were added with
idealized PH2 geometry, and the P-H bond lengths were restrained
to be ∼1.45(2) Å. In the final stage of least-squares refinement, all
non-hydrogen atoms were refined anisotropically. H atoms on C atoms
were generated by the program SHELXL-97. The positions of these
H atoms were calculated on the basis of the riding mode with thermal
parameters equal to 1.2 times that of the associated C atoms and
participated in the calculation of final R indices.
[RuII(Pc)(PMe2Ph)2] (8). Yield: 49%. 1H NMR (300 MHz,
CDCl3): δ Pc 9.05 (m, 8H), 7.86 (m, 8H); Hp 6.63 (m, 2H); Hm
6.28 (m, 4H); Ho 4.35 (m, 4H); Me -2.09 (s, 12H). 31P{1H} NMR
(162 MHz, CDCl3): δ -1.3. UV-vis (3.7 × 10-5 M, CH2Cl2):
λmax (log ε) 306 (4.4), 428 (3.4) sh, 580 (3.8) sh, 634 (4.3) nm.
FAB MS: m/z 890 (M+), 752 ([M - PMe2Ph]+), 614 ([M -
2PMe2Ph]+). Anal. calcd for C48H38N8P2Ru·0.5CH2Cl2: C, 62.48;
H, 4.22; N, 12.02. Found: C, 62.68; H, 4.30; N, 11.96.
1
[RuII(Pc)(PMePh2)2] (10a). Yield: 87%. H NMR (400 MHz,
CDCl3): δ Pc 9.00 (m, 8H), 7.85 (m, 8H); Hp 6.66 (m, 4H); Hm
6.29 (m, 8H); Ho 4.44 (m, 8H); Me -1.84 (s, 6H). 31P{1H} NMR
(162 MHz, CDCl3): δ -0.5. UV-vis (2.1 × 10-5 M, CH2Cl2):
λmax (log ε) 296 (4.5), 420 (3.5) sh, 579 (4.0) sh, 637 nm (4.4).
FAB MS: m/z 1014 (M+), 814 ([M - PMePh2]+), 614 ([M -
2PMePh2]+). Anal. calcd for C58H42N8P2Ru·1.5CH2Cl2: C, 62.61;
H, 3.97; N, 9.82. Found: C, 62.73; H, 4.05; N, 9.95.
[RuII(Pc)(P(Bun)Ph2)2] (10b). Yield: 50%. 1H NMR (300 MHz,
CDCl3): δ Pc 8.99 (m, 8H), 7.84 (m, 8H); Hp 6.70 (m, 4H); Hm 6.28
(m, 8H); Ho 4.40 (m, 8H); Bun 0.07 (m, 4H), -0.14 (m, 6H), -1.34
(m, 4H), -1.85 (m, 4H). 31P{1H} NMR (162 MHz, CDCl3): δ 9.3.
UV-vis (9.3 × 10-5 M, CH2Cl2): λmax (log ε) 302 (4.5), 421 (3.7) sh,
580 (4.2) sh, 639 (4.5) nm. FAB MS: m/z 1098 (M+), 856 ([M -
P(Bun)Ph2]+), 614 ([M - 2P(Bun)Ph2]+). Anal. calcd for C64H54N8-
P2Ru·1.5CH2Cl2: C, 64.19; H, 4.69; N, 9.14. Found: C, 64.23; H, 4.78;
N, 9.02.
1
[RuII(Pc)(PBnPh2)2] (10c). Yield: 62%. H NMR (400 MHz,
CDCl3): δ Pc 9.03 (m, 8H), 7.87 (m, 8H); Hp 6.67 (m, 4H); Hm, H′p
6.21 (m, 10H); H′m 6.00 (m, 4H); H′o 4.82 (m, 4H); Ho 4.37 (m, 8H);
Bn CH2 -0.59 (s, 4H). (H′p, H′m, and H′o are the phenyl signals of a
Bn group). 31P{1H} NMR (162 MHz, CDCl3): δ 16.2. UV-vis (4.5
× 10-5 M, CH2Cl2): λmax (log ε) 299 (4.5), 421 (3.4), 581 (3.9), 640
(4.4) nm. FAB MS: m/z 1166 (M+), 890 ([M - PBnPh2]+), 614 ([M
- 2PBnPh2]+). Anal. calcd for C70H50N8P2Ru ·CH2Cl2: C, 68.16; H,
4.19; N, 8.96. Found: C, 68.47; H, 4.19; N, 9.02.
[RuII(Pc)(P(CH2CHdCH2)Ph2)2] (10d). Yield: 60%. 1H NMR
(300 MHz, CDCl3): δ Pc 9.01 (m, 8H), 7.87 (m, 8H); Hp 6.70 (m,
4H); Hm 6.27 (m, 8H); Ho 4.42 (m, 8H); Hb, Hc, Hd 3.61 (m, 2H),
3.23 (m, 4H); Ha -1.09 (d, J ) 5.31 Hz, 4H). 31P{1H} NMR (162
MHz, CDCl3): δ 12.2. UV-vis (1.2 × 10-5 M, CH2Cl2): λmax (log
ε) 296 (4.5), 420 (3.5) sh, 580 (3.9) sh, 639 (4.3) nm. FAB MS:
m/z 1066 (M+), 840 ([M - P(CH2CH)CH2)Ph2]+), 614 ([M -
2P(CH2CH)CH2)Ph2]+). Anal. calcd for C62H46N8P2Ru·CH2Cl2:
C, 65.74; H, 4.20; N, 9.74. Found: C, 65.69; H, 4.05; N, 9.88.
Acknowledgment. This work was supported by The
University of Hong Kong (Seed Funding for Basic Research),
Hong Kong Research Grants Council (HKU7026/04P), and
the University Grants Committee of the Hong Kong SAR
of China (Area of Excellence Scheme, AoE/P-10/01).
1
[RuII(Pc)(P(CH2CtCMe)Ph2)2] (10e). Yield: 58%. H NMR
Supporting Information Available: Figure S1 and positional
and thermal parameters and bond lengths and angles for 1a,
2b·2CH2Cl2, 3b,c, 4, and 5b·2CH2Cl2 in CIF format. This material
is available free of charge via the Internet at http://pubs.acs.org.
(300 MHz, CDCl3): δ Pc 9.00 (m, 8H), 7.85 (m, 8H); Hp 6.70 (m,
4H); Hm 6.28 (m, 8H); Ho 4.42 (m, 8H); Me 0.60 (s, 6H); Ha -1.00
(s, 4H). 31P{1H} NMR (162 MHz, CDCl3): δ 14.4. UV-vis (3.4 ×
10-5 M, CH2Cl2): λmax (log ε) 296 (4.6), 420 (3.5) sh, 581 (4.0) sh,
640 (4.5) nm. FAB MS: m/z 1090 (M+), 852 ([M
-
IC800484K
P(CH2CtCMe)Ph2]+), 614 ([M - 2P(CH2CtCMe)Ph2]+). Anal.
calcd for C64H46N8P2Ru·1.5CH2Cl2: C, 64.62; H, 4.06; N, 9.20. Found:
C, 64.86; H, 4.03; N, 9.33.
(26) Program for the Solution of Crystal Structures: Sheldrick, G. M.
SHELXS-97; University of Go¨ttingen: Go¨ttingen, Germany, 1997.
(27) Program for the Refinement of Crystal Structures: Sheldrick, G. M.
SHELXL-97; University of Go¨ttingen: Go¨ttingen, Germany, 1997.
1
[RuII(Pc)(P(CHdCdCH2)Ph2)2] (10f). Yield: 44%. H NMR
(400 MHz, CDCl3): δ Pc 9.00 (m, 8H), 7.83 (m, 8H); Hp 6.63 (m,
Inorganic Chemistry, Vol. 47, No. 20, 2008 9181