Preparation and characterization of palladium and platinum complexes bearing 1,8-bis[(diphenylphosphino)methyl]naphthalene

Article abstract of DOI:10.1039/b100860i

Reaction of MCl₂(cod) (M = Pd, Pt) with 1,8-bis[(diphenylphosphino)methyl]naphthalene (1,8-dpmn) gave MCl₂(1,8-dpmn) 1 (M = Pd), 2 (M = Pt), as confimed by X-ray analyses. Complex 1 reacted with xylyl isocyanide a (XylNC) in the presence of NaPF₆ to give [Pd(1,8-dpmn)(XylNC)₂](PF₆)₂ 3a. Reactions of dinuclear complexes [M₂(RNC)₆](PF₆)₂ (4: M = Pd, 5: M = Pt; R = Xyl (a) or 2,4,6-Me₃C₆H₂ (b) (Mes)) with one or two equiv. of 1,8-dpmn gave [M₂(1,8-dpmn)(RNC)₄](PF₆)₂ 6 (M = Pd) and 7 (M = Pt), or [M₂(1,8-dpmn)₂(RNC)₂](PF₆) ₂ 8 (M = Pd) and 9 (M = Pt). The structures of 6b, 7b and 8b were confirmed by X-ray analyses. Reaction of [Pd₂Cl₂(XylNC)₄] with two equiv. of 1,8-dpmn in the presence of NaPF₆ gave 8a, whereas the reaction in the presence of NH₄PF₆ produced 10a together with 7a. It was confirmed by an X-ray analysis of 10a that the crystal lattice is constructed by two types of cations (3a and two 2,2,6,6-tetramethyl-4-piperidonium) and four PF₆ anions. Photochemical reaction of 6a or 8a in CH₂Cl₂ led to cleavage of the Pd-Pd bond, giving [PdCl(XylNC)₃](PF₆) and [PdCl(1,8-dpmn)(XylNC)](PF₆).

Full text of DOI:10.1039/b100860i

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Preparation and characterization of palladium and platinum
complexes bearing 1,8-bis[(diphenylphosphino)methyl]naphthalene
Yasuhiro Yamamoto,*a Yasushi Fukui,a Katsuaki Matsubara,a Hiroya Takeshima,a
Fumiyoshi Miyauchi,a Tomoaki Tanaseb and Gaku Yamamotoc
a Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi,
Chiba 274-8510, Japan. E-mail: yamamoto@chem.sci.toho-u.ac.jp
b Department of Chemistry, Faculty of Science, Nara Women’s University,
Kitauoya-higashi-machi, Nara, 630–8285, Japan
c Department of Chemistry, Faculty of Science, Kitazato University, Kitazato, Sagamihara,
Kanagawa 228-8555, Japan
Received 24th January 2001, Accepted 4th April 2001
First published as an Advance Article on the web 16th May 2001
Reaction of MCl2(cod) (M = Pd, Pt) with 1,8-bis[(diphenylphosphino)methyl]naphthalene (1,8-dpmn) gave
MCl2(1,8-dpmn) 1 (M = Pd), 2 (M = Pt), as confirmed by X-ray analyses. Complex 1 reacted with xylyl isocyanide
a (XylNC) in the presence of NaPF6 to give [Pd(1,8-dpmn)(XylNC)2](PF6)2 3a. Reactions of dinuclear complexes
[M2(RNC)6](PF6)2 (4: M = Pd, 5: M = Pt; R = Xyl (a) or 2,4,6-Me3C6H2 (b) (Mes)) with one or two equiv. of 1,8-
dpmn gave [M2(1,8-dpmn)(RNC)4](PF6)2 6 (M = Pd) and 7 (M = Pt), or [M2(1,8-dpmn)2(RNC)2](PF6)2 8 (M = Pd)
and 9 (M = Pt). The structures of 6b, 7b and 8b were confirmed by X-ray analyses. Reaction of [Pd2Cl2(XylNC)4] with
two equiv. of 1,8-dpmn in the presence of NaPF6 gave 8a, whereas the reaction in the presence of NH4PF6 produced
10a together with 7a. It was confirmed by an X-ray analysis of 10a that the crystal lattice is constructed by two types
of cations (3a and two 2,2,6,6-tetramethyl-4-piperidonium) and four PF6 anions. Photochemical reaction of 6a or 8a
in CH2Cl2 led to cleavage of the Pd–Pd bond, giving [PdCl(XylNC)3](PF6) and [PdCl(1,8-dpmn)(XylNC)](PF6).
Introduction
Results and discussion
1,8-Bis(diphenylphosphino)naphthalene (1,8-dppn) and its
derivatives are rigid in their manner of co-ordination because
of the direct binding of the phosphorus atoms to the naphth-
alene rings, and form chelate complexes, MCl2(1,8-dppn) (M =
Pd, Pt).1,2 1,8-Bis[(diphenylphosphino)methyl]naphthalene (1,8-
dpmn), formed by introduction of a methylene group between
the naphthalene ring and phosphorus atom, is less rigid than
1,8-dppn and has the potential for co-ordination modes other
than chelation.
We have studied the electrochemical or chemical preparation
of di-, tri-, and poly-nuclear platinum and palladium complexes
of isocyanides bearing various diphosphines3–11 or triphos-
phine.12 Controlled potential electrolysis of [Pt(diphos)-
(RNC)2]2ϩ at a mercury-pool electrode gave [Pt2(diphos)2-
(RNC)2]2ϩ(diphos = Ph2(CH2)nPPh2 (n = 2–4); R = 2,6-Me2C6H3
(Xyl), 2,4,6-Me3C6H2 (Mes)), [Pt2(µ-dppm)2(RNC)2]2ϩ, [Pt3-
(µ-dppm)2(RNC)4]2ϩ (A-frame) and [HgPt6(dppb)2(RNC)8],
depending on the coulometric conditions or diphosphines.
One-electron reduction of [Pd(diphos)(RNC)2]2ϩ (diphos =
Ph2(CH2)nPPh2, n = 2–4) at a platinum electrode formed the
chelate dimers [Pd2(diphos)2(RNC)2]2ϩ.6 Chemical reduction of
[Pt(dpphex)(RNC)2]2ϩ (dpphex = Ph2P(CH)6PPh2) with Na/Hg
also gave the Pt–Hg mixed cluster [Hg2Pt6(dpphex)3(RNC)6].5
These complexes could be prepared by the substitution
reactions of [M2(RNC)4]2ϩ (M = Pd, Pt) or [Pt3(RNC)8]2ϩ with
appropriate diphosphines.
Reactions of MCl2(cod) (M = Pd, Pt) with 1,8-dpmn gave
MCl2(1,8-dpmn) (1: M = Pd, 2: M = Pt) in good yields. X-Ray
analyses of 1 and 2 were undertaken. The perspective drawings
of 1 and 2 with the atomic numbering schemes are given in Figs.
1 and 2. Selected bond lengths and angles are listed in Table 1.
Complexes 1 and 2 are isomorphous. The molecules have cis
structures with bite angles (P–M–P) of 93.5Њ for 1 and 94.4Њ
for 2, compared with those of RuH2(CO)(PPh3)(1,8-dpmn)
(95.96Њ)13 and dppb (Ph2P(CH2)4PPh2) complexes (94.51Њ).14
The dihedral angles between the MP2Cl2 plane and the naphth-
alene ring are 89.0Њ for 1 and 86.5Њ for 2, respectively. The
MP2Cl2 plane is also perpendicular to two phenyl rings among
four phenyl rings (86–88Њ). The average Pt–P bond length of
2.236 Å is shorter than the average Pd–P length of 2.263 Å,
We report here the preparations and characterization of
four-co-ordinate palladium and platinum complexes bearing
1,8-dpmn. The chemistry of metal complexes bearing 1,8-dpmn
is limited to the synthesis of ruthenium complexes of 1,8-dpmn
by Tin et al.13
Fig. 1 Structure of [PdCl2(1,8-dpmn)] 1.
DOI: 10.1039/b100860i
J. Chem. Soc., Dalton Trans., 2001, 1773–1781
This journal is © The Royal Society of Chemistry 2001
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Table 1 Selected bond lengths (Å) and angles (Њ) for cis-PdCl2(1,8-dpmn) 1 and cis-PtCl2(1,8-dpmn) 2
(a) cis-PdCl2(1,8-dpmn) 1
Pd(1)–Cl(1)
Pd(1)–P(2)
C(1)–C(3)
2.358(5)
2.268(5)
1.53(2)
Pd(1)–Cl(2)
P(1)–C(2)
C(2)–C(11)
2.346(5)
1.86(2)
1.51(2)
Pd(1)–P(1)
P(2)–C(1)
2.261(6)
1.87(2)
Cl(1)–Pd(1)–Cl(2)
Cl(2)–Pd(1)–P(1)
Pd(1)–P(1)–C(2)
P(1)–C(2)–C(11)
88.4(2)
88.2(2)
122.1(6)
115(1)
Cl(1)–Pd(1)–P(1)
Cl(2)–Pd(1)–P(2)
Pd(1)–P(2)–C(1)
171.8(2)
171.2(2)
122.9(6)
Cl(1)–Pd(1)–P(2)
P(1)–Pd(1)–P(2)
P(2)–C(1)–C(3)
88.4(2)
93.5(2)
111(1)
(b) cis-PtCl2(1,8-dpmn) 2
Pt(1)–Cl(1)
Pt(1)–P(2)
C(1)–C(3)
2.355(7)
2.238(7)
1.49(3)
Pt(1)–Cl(2)
P(1)–C(1)
C(2)–C(11)
2.353(7)
1.86(3)
1.55(3)
Pt(1)–P(1)
P(2)–C(2)
2.234(7)
1.81(3)
Cl(1)–Pt(1)–Cl(2)
Cl(2)–Pt(1)–P(1)
Pt(1)–P(1)–C(1)
P(2)–C(2)–C(11)
86.3(3)
89.0(3)
120.8(9)
115(2)
Cl(1)–Pt(1)–P(2)
Cl(2)–Pt(1)–P(2)
Pt(1)–P(2)–C(2)
89.3(3)
171.4(3)
120(1)
Cl(1)–Pt(1)–P(1)
P(1)–Pt(1)–P(2)
P(1)–C(1)–C(3)
171.9(3)
94.4(3)
119(2)
Fig. 3 The 31P{1H} NMR spectrum of 7a.
treated with an equiv. of 1,8-dpmn, yellow crystals formulated
as [M2(1,8-dpmn)(RNC)4](PF6)2 (6: M = Pd; 7: M = Pt) were
formed (Scheme 2). The IR spectra of 6 and 7 showed a strong
band at ca. 2165 cmϪ1 and a very weak band at ca. 2190 cmϪ1
,
1
due to the N–C triple bond. The H NMR spectra of 6 and 7
showed the presence of four kinds of isocyanide ligands,
suggesting that all isocyanide ligands are nonequivalent. The
31P{1H} NMR spectra of 6 showed a doublet around δ 21 and
13 with 2JPPЈ = 54.5 Hz, respectively; the former is assignable to
the phosphorus atom in a trans-position to the Pd atom and the
latter to that in a cis-position, based on the chemical shift in
the 31P{1H} NMR spectrum of [Pt2(1,8-dpmn)(RNC)4](PF6)2
(vide infra).
Fig. 2 Structure of [PtCl2(1,8-dpmn)] 2.
The 31P{1H} NMR spectrum of [Pt2(1,8-dpmn)(XylNC)4]-
(PF6)2 7a indicated two sets of resonances centered at δ 28.0 and
9.2, which are accompanied by satellite peaks due to 195Pt (I =
1/2) atom (Fig. 3). The observed spectrum is explicable as a
combination of four isotopomers, P2Pt–Pt, P2Pt–195Pt, P2195Pt–
Pt and P2195Pt–195Pt (their ratios calculated from the natural
abundance are 4 : 2 : 2 : 1). From the higher field set (A) cen-
1
2
2
tered at δ 9.2, the values of JPPt, JPPt and JPPЈ were estimated
to be 3076, 53 and 25 Hz, respectively. From the lower field set
1
2
2
(B) centered at δ 28.0, the values of JPЈPt, JPЈPt and JPPЈ were
estimated to be 2275, 440 and 25 Hz, respectively. From analogy
to the 31P{1H} NMR spectra of [Pt2(diphos)2(RNC)2](PF6)2
bearing the chelate structure and comparison with the values of
Scheme 1 Reaction of cis-PdCl2(1,8-dpmn) 1 with xylyl isocyanide in
the presence of NaPF6. The PF6 anions are omitted for clarity.
2
the JPPt coupling constants, the resonance A was assigned to
the phosphorus atom occupying the position cis to the Pt–Pt
bond and the resonance B, to the phosphorus atom in the
trans position to the Pt–Pt bond. A similar pattern was
observed in 7b.
X-Ray crystallographic analyses of 6b and 7b were under-
taken. The perspective drawings of the complex cations of 6b
and 7b with the atomic numbering schemes are given in Figs. 4
and 5. Some selected bond lengths and angles are listed in Table
2. The complex cations consist of two palladium or platinum
atoms joined by a metal–metal σ-bond. The Pd(2) or Pt(2) atom
whereas the average M–Cl bond lengths for Pd and Pt com-
plexes are identical.
Complex 1 was treated with xylyl isocyanide (XylNC) in
the presence of NaPF6 at room temperature to give [Pd(1,8-
dpmn)(XylNC)2](PF6)2 3a in high yield (Scheme 1). The IR
spectrum showed a characteristic band at 2213 cmϪ1, corre-
sponding to the terminal isocyanide groups.
When dimeric palladium or platinum complexes [M2(RNC)6]-
(PF6)2 (4: M = Pd, 5: M = Pt; a: R = Xyl, b: R = Mes) were
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Scheme 2 Reaction of [M2(RNC)4](PF6)2 (M = Pd, Pt) with 1,8-dpmn. The PF6 anions are omitted for clarity.
mizing the repulsion between the ligands. Similar structures
have been observed in the nonbridged dimer.
The naphthalene ring has a dihedral angle of 69(1)Њ for the
Pd(2)P(1)P(2)C(31) plane compared to 108(1)Њ for the
Pt(2)P(1)P(2)C(31) plane. The Pd(1)–Pd(2) (2.568(3) Å) and
Pt(1)–Pt(2) (2.61(4) Å) bond lengths are significantly longer
than those for isocyanide dimers without phosphine ligands,
[Pd2Cl2(tBuNC)4] (2.532(2) Å),15 [Pd2(MeNC)6](PF6)2 (2.531(1)
Å),16–18 [Pd2I2(MeNC)4] (2.533(1) Å)19 and [Pt2Cl2(2,4-tBu2-6-
MeC6H2NC)4] (2.532(2) Å).20 The Pd(2)–P(1) bond length of
2.351(7) Å and Pt(2)–P(2) bond length of 2.39(4) Å in a trans-
position to the metal atom are longer than those found in
another M–P bond in a cis-position, due to the strong trans-
influence of the metal–metal bond. The P–M–P bite angles for
both complexes are typical. The average M(2)–M(1)–C bond
angles in the M(1)C3 plane are 84Њ for both 6b and 7b and the
M(1)–M(2)–C(31) angles in the M(2)P2C(31) plane are
72.8(10)Њ for 6b and 80(1)Њ for 7b. Each isocyanide ligand is
bent toward another metal atom. The large inward bend of the
latter depends on the steric bulk of the diphosphine. This trend
has been noted in [M2(diphos)2(RNC)2](PF6)2 (M = Pd,9 Pt10).
The M–C–N and C–N–C bond angles, except Pt(1)–C(1)–N(1)
(165(4)Њ), C(1)–N(1)–C(2) (166(4)Њ) and C(11)–N(2)–C(12)
(167(4)Њ), are linear (171–179Њ).
Fig. 4 Structure of [Pd2(1,8-dpmn)(MesNC)4](PF6)2 6b. The PF6
anions are omitted for clarity.
When the reactions between [M2(RNC)8](PF6)2 and 1,8-
dpmn were carried out in a 1 : 2 molar ratio, further substitu-
tion reactions occurred to form [M2(1,8-dpmn)2(RNC)2](PF6)2
(8: M = Pd; a: R = Xyl; b: R = Mes. 9: M = Pt; a: R = Xyl; b:
R = Mes) (Scheme 2). The IR spectra showed the band due to
the terminal isocyanide groups at ca. 2130 cmϪ1. It is reason-
able, given the high electron donation ability of diphosphines,
that the v(N᎐C) frequency is shifted to ca. 30 cmϪ1 lower energy
᎐
᎐
1
than for the monochelate complexes 6 and 7. The H NMR
spectra of 8 and 9 showed the presence of only one type of
isocyanide ligand.
The 31P{1H} NMR spectra of 8 showed two sets of reson-
ances at δ ca. 9.0 and 20.0. The 31P{1H} NMR spectrum of 8b
has been satisfactorily simulated using a computer analysis
based on a AAЈXXЈ spin system. The observed and calculated
31P{1H} NMR spectrum for 8b is depicted in Fig. 6, but
attempts to simulate the spectrum 8a were unsuccessful due to
spectral overlapping. Analogously, the analyses of the 31P{1H}
NMR spectra of 9 were unsuccessful because of the very com-
plicated patterns.
A structure of the complex cation of 8b with the atomic
numbering scheme is given in Fig. 7. Selected bond lengths and
angles are listed in Table 3. The molecule has a crystallographi-
cally imposed inversion center in the middle of the Pd ؒ ؒ ؒ Pd*
vector. The complex cation consists of two palladium atoms
joined by a Pd–Pd σ-bond. Each palladium atom is surrounded
by two phosphorus atoms from the bidentate 1,8-dpmn ligand,
a terminal carbon atom from the isocyanide, and another
palladium atom in a nearly planar array. The dihedral angle
between two [PdP2C] co-ordination planes is 79.8Њ, being
smaller by 6Њ than those of [Pd2(MesNC)2(dppp)2](PF6)2 (86Њ)9
and [Pt2(MesNC)2(dppp)2](PF6)2 (86Њ).
Fig. 5 Structure of [Pt2(1,8-dpmn)(MesNC)4](PF6)2 7b. The PF6
anions are omitted for clarity.
is co-ordinated by two phosphorus atoms of a bidentate 1,8-
dpmn ligand, a terminal carbon atom of isocyanide and
another Pd(1) or Pt(1) atom, which is surrounded by the
terminal carbon atoms of three isocyanide ligands. The
structures are in good agreement with the nonequivalence of
isocyanide ligands in the 1H NMR spectra.
A dihedral angle between the [MP2C] and [MC3] co-
ordination planes is 99(1)Њ for 6b and 83(1)Њ for 7b, nearly
perpendicular as observed in other dinuclear complexes, mini-
The Pd–Pd bond length of 2.670(3) Å is significantly longer
J. Chem. Soc., Dalton Trans., 2001, 1773–1781
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Table 2 Selected bond lengths (Å) and angles (Њ) for [Pd2(1,8-dpmn)(MesNC)4](PF6)2ؒ(CH3)2CO 6bؒ(CH3)2CO and [Pt2(1,8-dpmn)(MesNC)4](PF6)2
7b
(a) [Pd2(1,8-dpmn)(MesNC)4](PF6)2ؒ(CH3)2CO 6bؒ(CH3)2CO
Pd(1)–Pd(2)
Pd(1)–C(21)
Pd(2)–C(31)
C(21)–N(3)
2.568(3)
1.99(2)
1.85(3)
1.12(2)
Pd(1)–C(1)
Pd(2)–P(1)
C(1)–N(1)
C(31)–N(4)
2.07(3)
2.351(7)
1.15(3)
1.22(3)
Pd(1)–C(11)
Pd(2)–P(2)
C(11)–N(2)
2.02(2)
2.291(8)
1.12(2)
Pd(2)–Pd(1)–C(1)
C(1)–Pd(1)–C(11)
Pd(1)–Pd(2)–P(1)
P(1)–Pd(2)–P(2)
Pd(1)–C(1)–N(1)
C(11)–N(2)–C(12)
Pd(2)–C(31)–N(4)
P(2)–C(76)–C(74)
178.5(6)
Pd(2)–Pd(1)–C(11)
C(1)–Pd(1)–C(21)
Pd(1)–Pd(2)–P(2)
P(1)–Pd(2)–C(31)
C(1)–N(1)–C(2)
Pd(1)–C(21)–N(3)
C(31)–N(4)–C(32)
83.6(7)
97.1(9)
93.8(2)
101(1)
179(2)
178(2)
170(2)
Pd(2)–Pd(1)–C(21)
C(11)–Pd(1)–C(21)
Pd(1)–Pd(2)–C(31)
P(2)–Pd(2)–C(31)
Pd(1)–C(11)–N(2)
C(21)–N(3)–C(22)
P(1)–C(65)–C(66)
84.4(7)
167(1)
72.8(10)
163.1(9)
170(2)
175(2)
109(1)
94.9(10)
171.5(2)
93.2(3)
176(2)
172(3)
171(2)
106(1)
(b) [Pt2(1,8-dpmn)(MesNC)4](PF6)2 7b
Pt(1)–Pt(2)
Pt(1)–C(21)
Pt(2)–C(31)
C(21)–N(3)
2.61(4)
1.99(3)
2.03(5)
1.13(3)
Pt(1)–C(1)
Pt(2)–P(1)
C(1)–N(1)
C(31)–N(4)
1.97(6)
2.24(4)
1.08(7)
1.17(5)
Pt(1)–C(11)
Pt(2)–P(2)
C(11)–N(2)
1.83(3)
2.39(4)
1.22(3)
Pt(2)–Pt(1)–C(1)
C(1)–Pt(1)–C(11)
Pt(1)Pt(2)–P(1)
P(1)–Pt(2)–P(2)
Pt(1)–C(1)–N(1)
C(11)–N(2)–C(12)
Pt(1)–C(31)–N(4)
P(2)–C(66)–C(74)
176(1)
93(1)
94(1)
93.3(10)
165(4)
167(4)
173(2)
106(2)
Pt(2)–Pt(1)–C(11)
C(1)–Pt(1)–C(21)
Pt(1)–Pt(2)–P(2)
P(1)–Pt(2)–C(31)
C(1)–N(1)–C(2)
Pt(1)–C(21)–N(3)
C(31)–N(4)–C(32)
84(1)
97(1)
171(1)
168.7(8)
166(4)
175(4)
172(4)
Pt(2)–Pt(1)–C(21)
C(11)–Pt(1)–C(21)
Pt(1)–Pt(2)–C(31)
P(2)–Pt(2)–C(31)
Pt(1)–C(11)–N(2)
C(21)–N(3)–C(22)
P(1)–C(65)–C(67)
84(1)
167(2)
80(1)
92(1)
175(2)
171(3)
112(2)
Table 3 Selected bond lengths (Å) and angles (Њ) for [Pd2(1,8-dpmn)2(MesNC)2](PF6)2ؒ(CH3)2CO 8bؒ2(CH3)2CO
Pd(1)–Pd(2)
Pd(1)–C(1)
2.670(3)
1.95(2)
Pd(1)–P(1)
C(1)–N(1)
2.330(5)
1.18(2)
Pd(1)–P(2)
2.387(5)
Pd(1)*–Pd(1)–P(1)
P(1)–Pd(1)–P(2)
Pd(1)–C(1)–N(1)
P(2)–C(111)–C(101)
103.7(1)
Pd(1)–Pd(1)–P(2)
P(1)–Pd(1)–C(1)
C(1)–N(1)–C(11)
164.6(1)
171.2(5)
174(2)
Pd(1)*–Pd(1)–C(1)
P(2)–Pd(1)–C(1)
P(1)–C(112)–C(109)
72.4(5)
93.0(5)
109(1)
91.4(2)
167(1)
106(1)
Fig. 7 Structure of [Pd2(1,8-dpmn)2(MesNC)2](PF6)2 8b. The PF6
anions are omitted for clarity.
Fig. 6 (a) Observed and (b) calculated 31P{1H} NMR spectrum for
[Pd2(1,8-dpmn)2(MesNC)2](PF6)2 8b.
angle is 165.3Њ, comparable to that in [Pd2(XylNC)2(dppf)2]-
(PF6)2 (163.75Њ).
than those in the bis-diphosphine complexes, [Pd2(MesNC)2-
(dppp)2](PF6)2 (2.617(2) Å)9 and [Pd2(XylNC)2(dppen)2](PF6)2
The P(1)–Pd(1)–P(2) bite angle of 91.4(2)Њ is narrower than
that of 6b (93.2(3)Њ). The Pd(1)*–Pd(1)–C(1) angle of 72.4(5)Њ
is similar to the corresponding angles for 6b and 7b. A
characteristic feature is that the Pd(1)*–Pd(1)–P(1) angle of
103.7(1)Њ is wider by ca. 10Њ than those of the mono-substituted
diphosphine complexes 6b and 7b, minimizing the repulsive
(dppen = Ph PCH᎐CHPPh ) (2.602(1) Å)9 and [Pd2(XylNC)2-
᎐
2
2
(dppf)2](PF6)2
(dppf = 1,1Ј-bis(diphenylphosphino)ferrocene
(2.602(1) Å),21 probably due to minimization of the steric
repulsion between the naphthalene ring and the isocyanide
connected to another palladium atom. The average Pd–Pd–Pax
1776
J. Chem. Soc., Dalton Trans., 2001, 1773–1781

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Table 4 Selected bond lengths and angles for [{Pd(1,8-dpmn)(XylNC)2}{HN(CH2)2(CMe2)2CO}2](PF6)4 10a
[Pd(1,8-dpmn)(XylNC)2]2ϩ
Pd(1)–P(1)
Pd(1)–C(46)
2.312(7)
1.96(3)
Pd(2)–P(2)
C(37)–N(1)
2.305(8)
1.15(3)
Pd(1)–C(37)
C(46)–N(2)
1.89(3)
1.15(3)
P(1)–Pd(1)–P(2)
P(2)–Pd(1)–C(37)
Pd(1)–C(37)–N(1)
C(36)–N(2)–C(47)
93.3(3)
91.1(9)
175(2)
178(2)
P(1)–Pd(1)–C(37)
P(2)–Pd(1)–C(46)
C(37)–N(1)–C(38)
P(1)–C(11)–C(1)
171.2(9)
P(1)–Pd(1)–C(46)
C(37)–Pd(1)–C(46)
Pd(2)–C(46)–N(2)
P(2)–C(24)–C(9)
88.0(7)
86(1)
176(2)
110(1)
172.4(8)
169(2)
115(1)
[2,2,6,6-Tetramethyl-4-piperidonium]
N(3)–C(57)
N(4)–C(66)
1.49(4)
1.48(3)
N(3)–C(60)
N(4)–C(69)
1.51(4)
1.52(4)
C(55)–O(1)
C(64)–O(2)
1.29(4)
1.11(3)
Scheme 3 Reaction of [Pd2Cl2(XylNC)4] with 1,8-dpmn in the presence of NH4PF6 or NaPF6 (L = XylNC). The PF6 anions are omitted for clarity.
interaction with another 1,8-dpmn ligand. The structure of
platinum complex 9 is considered to be similar to that of 8.
When two equiv. of 1,8-dpmn was added to a CH2Cl2
solution of trinuclear complex [Pd3(XylNC)8](PF6)2 at room
temperature, the reaction solution changed rapidly from yellow
to violet and finally to yellow. This color change suggested
the occurrence of a substitution reaction with 1,8-dpmn but
attempts to isolate the violet species were unsuccessful because
the change proceeded very quickly, suggesting that a trinuclear
complex bearing diphosphine is very unstable. This trend has
also been observed in the reaction of [Pd3(XylNC)8](PF6)2 with
the bulky phosphine, [2,6-(MeO)2C6H3)]3P. 22
Reactions of [Pd2Cl2(XylNC)4] with 1,8-dpmn in the presence of
NaPF6 or NH4PF6
When the neutral dinuclear complex [Pd2Cl2(XylNC)4], was
treated in acetone, with two equiv. of 1,8-dpmn in the presence
of excess NaPF6, 8a was obtained. However on treatment with
an excess of NH4PF6, two complexes, 8a and 10a formulated
as [{Pd(1,8-dpmn)(XylNC)2}{HN(CH2)2(CMe2)2CO}2](PF6)4,
were formed (Scheme 3).
It was confirmed by X-ray analysis that 10a consists of two
kinds of cations, [Pd(1,8-dpmn)(XylNC)2]2ϩ and two 2,2,6,6-
tetramethyl-4-piperidonium, and four PF6 anions (Fig. 8 and
Table 4). It is very rare that two kinds of cations are incorp-
orated into the crystal lattice. The complex cation, [Pd(1,8-
dpmn)(XylNC)2]2ϩ was surrounded by two phosphorus atoms
of 1,8-dpmn and the terminal carbon atoms of two isocyanide
ligands. The dihedral angle between the PdP2C2 and naphth-
alene planes is 104.3Њ, comparable with that for 7b. The P(1)–
Pd–P(2) bite angle is 93.3(3)Њ, comparable with those of 1 and
2. The piperidonium cation adopted a typical chair-form. The
bond lengths and angles fall within the usual values.
The IR spectrum of 10a showed characteristic absorption
bands at 3198, 3135, 2218 and 1725 cmϪ1. The band at ca. 2200
cmϪ1 is assigned to terminal isocyanide ligands. Two bands
around 3160 cmϪ1 and the bond at 1725 cmϪ1 are due to the
Fig. 8 Structures of two cations, [Pd(1,8-dpmn)(XylNC)2]2+ and
2,2,6,6-tetramethyl-4-piperidonium in 10a. The PF6 anions are omitted
for clarity.
N–H and C᎐O groups, respectively. The presence of PF anions
᎐
6
1
was confirmed by a broad band at 847 cmϪ1. In the H NMR
spectrum, the methyl and methylene protons of the piperido-
nium cation and o-methyl protons of isocyanide appeared at
δ 1.69, 2.87 and 1.99, respectively. Multiplets of the P–CH2
protons appeared at δ ca. 4.63 and ca. 5.86. The 31P{1H} NMR
spectrum indicated a singlet at δ 30.3, in close agreement with
that of 3a. After several crystallizations of 10a 3a and a piper-
idonium cation as a PF6 salt could be isolated separately.
Preparation of complex 10a consists of an initial formation
of 8a, accompanied by cleavage of the metal–metal bond and
generation of NH4Cl as shown in Scheme 4. This mechanism
has also been observed in the reaction of [Pd2Cl2(XylNC)4] with
tris(2,6-dimethoxyphenyl)phosphine (L) in the presence of
NH4PF6 to give [PdCl(L)(XylNC)2](PF6).22 Finally, complex 3a
J. Chem. Soc., Dalton Trans., 2001, 1773–1781
1777

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Scheme 4 A possible path for the formation of 10a. The PF6 anions are omitted for clarity. L = XylNC; P∩ P = 1,8-dpmn.
was obtained by the reaction of [PdCl(1,8-dpmn)(XylNC)]-
(PF6) with xylyl isocyanide. In order to examine the origin of
2,2,6,6-tetramethyl-4-piperidonium, a mixture of NH4PF6 and
acetone was treated at room temperature for 24 h and led to
the formation of a PF6 salt of 2,2,6,6-tetramethyl-4-piper-
idonium, [HN(CH2)2(CMe2)2CO](PF6), in high yield, suggest-
ing that the palladium complex is unnecessary for the formation
of a piperidonium salt. No piperidonium derivative was
obtained when the reaction was carried out for a short time. In
fact, a short reaction gave only 8a. The reaction consists of an
amination of NH3, generated by an equilibrium of NH4PF6, to
a diol arising from the trimerization of acetone, accompanied
by a ring closure (Scheme 4).
Scheme 5 Photochemical reactions of 6a and 8a. The PF6 anions are
omitted for clarity. P∩ P = 1,8-dpmn.
Isocyanides,23 1,8-bis(dichloromethyl)naphthalene,24 [Pd2Cl2-
(RNC)4],25 [Pd2(RNC)6](PF6)2,20 [Pt2(RNC)6](PF6)2,20 and
[Pd3(RNC)8](PF6)2 were prepared according to the literature.
Photochemical reactions of dinuclear palladium complexes
20
In the UV-vis spectra of 6 and 8, the lowest energy absorption
band appeared at ca. 385 nm for 6 and ca. 460 nm for 8,
assigned to the σ→σ* transition of the Pd–Pd bond. It is
reasonable, given the high electron-donating ability of diphos-
phines, that the metal–metal bonds of 8 are weaker than those
of 6. This was traced back to the Pd–Pd bond lengths;
the Pd–Pd length is 2.568 Å for 6b and 2.670 Å for 8b. The
σ→σ* transitions of [Pd2(diphos)2(RNC)2](PF6)2 (diphos =
Ph2P(CH2)nPPh2; n = 2–4), having a structure similar to 8, have
been observed in the range from 421 to 434 nm,9 suggesting that
1,8-dpmn is a stronger electron-donating ligand than diphos-
phines bearing methylene groups, such as dppe, dppp, etc. This
observation is in agreement with the fact that the bond length
of 8b is longer than that found for [Pd2{Ph2P(CH2)3PPh2}2-
(XylNC)2](PF6)2.
When 6a was irradiated in CH2Cl2, the solution changed
from yellow to colorless. The σ→σ* transition around 385 nm
decreased and finally no appreciable absorption was observed
in the region λ > 380 nm. This reaction was monitored
spectroscopically, and the formation of two complexes,
[PdCl(XylNC)3](PF6) and [PdCl(1,8-dpmn)(XylNC)](PF6), was
confirmed (Scheme 5). Photochemical reaction of 8a also
showed a similar color-change and cleaved a Pd–Pd bond to
give [PdCl(1,8-dpmn)(XylNC)](PF6). The bond-cleavage rate
of 8a is faster than that of 6a.
Dichloromethane was distilled over CaH2 and diethyl ether was
distilled over LiAlH4. The IR spectra were measured on an
1
FT/IR-5300 instrument. The H NMR spectra were measured
at 250 MHz and 31P{1H}-NMR spectra were measured at 101
MHz using 85% H3PO4 as an external reference.
Syntheses
Preparation of 1,8-bis[(diphenylphosphino)methyl]naphth-
alene. Triphenylphosphine (7.6 g, 29.0 mmol) and lithium (0.6
g, 86.5 mmol) in tetrahydrofuran (THF) (40 mL), were stirred
for one day at room temperature, and lithium was removed
by filtration. tert-Butyl chloride (3.4 mL, 31 mmol) in THF
(10 mL) was added to the ice cooled solution which was then
heated at reflux for 10 min. After cooling in an ice-bath, 1,8-
[bis(dichloromethyl)]naphthalene (3.5 g, 15.6 mmol) in THF
(40 mL) was added dropwise and the mixture was refluxed for
30 min. The solvent was removed and a mixture of H2O (200
mL) and Et2O (200 mL) was added to form white solids. The
solids were filtered and washed with EtOH to give 1,8-dpmn
(3.0 g, 37%). 1H NMR (CDCl3): δ 4.21 (d, PCH2, 4H), 6.6–7.7
(c, napthalene, 26H). 31P{1H} NMR (CDCl3): δ Ϫ11.4 (s).
Anal. calc. for C36H30P2: C, 82.43; H, 5.78. Found: C, 82.62; H,
5.55%.
Preparation of PdCl2(1,8-dpmn)ؒ1.5CH2Cl2 1ؒ1.5CH2Cl2. To
a solution of PdCl2(cod) (50 mg, 0.18 mmol) in CH2Cl2 (5 mL),
1,8-dpmn (96 mg, 0.18 mmol) in CH2Cl2 (10 mL) was added
Experimental
All reactions were carried out under a nitrogen atmosphere.
1778
J. Chem. Soc., Dalton Trans., 2001, 1773–1781

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at room temperature. After stirring for 2 h, the mixture was
filtered on a glass filter (G4) and the solvent was concentrated
to ca. 3 mL and diethyl ether was added to give pale yellow
crystals of 1ؒ1.5CH2Cl2 (112 m, 77%). 1H NMR (CDCl3): δ 4.97
(d, JPH = 11.3 Hz, 4H, CH2), 5.27 (s, CH2Cl2), 7.02–7.93 (m,
26H, napthalene). 31P NMR (CDCl3): δ 33.4. Anal. calc. for
C36H30P2Cl2Pdؒ1.5CH2Cl2: C,54.31; H, 4.01. Found: C, 53.81;
H, 4.27%.
(s, o-Me, 6H), 4.38 (c, CH2, 2H), 5.45 (c, CH2, 2H), 6.8–7.9 (m,
Ph, 54H). 31P{1H} NMR(CD3COCD3): δ 9.17 (1JPЈPt = 3076 Hz,
2
2
2JPЈPt = 53 Hz, JPPЈ = 25 Hz), 28.0 (1JPЈPt = 2275 Hz, JPЈPt = 440
2
1
Hz, JPPЈ = 25 Hz), Ϫ143.4 (sep. JPF = 710 Hz). Anal. calc. for
C72H66N4P4F12Pt2: C, 50.02; H, 3.85; N, 3.24. Found: C, 50.90;
H, 4.00; N, 3.09%.
Preparation of [Pt2(1,8-dpmn)(MesNC)4](PF6)2 7b. Pale
yellow crystals of 7b (72%) were prepared from the reaction of
Preparation of PtCl2(1,8-dpmn)ؒ3H2O 2ؒ3H2O. To a solution
of PtCl2(cod) (59 mg, 0.16 mmol) in CH2Cl2 (5 mL), 1,8-dpmn
(84 mg, 0.16 mmol) in CH2Cl2 (10 mL) was added at room
temperature. After stirring for 2 h, the solvent was removed
under reduced pressure and the residue was crystallized from
CH2Cl2 and acetone to give white crystals of 2ؒ3H2O (58 mg,
43%). Anal. calc. for C36H30P2Cl2Ptؒ3H2O: C, 51.19; H, 4.30.
Found: C, 50.56; H, 3.87%.
[Pt2(MesNC)6](PF6)2 with 1,8-dpmn. IR (Nujol): 2206 (w), 2170
1
(st) (N᎐C), 835 (PF ) cmϪ1. H NMR (CDCl3): δ 1.79, 1.99,
᎐
᎐
6
2.02, 2.19 (s, o-Me, 24H), 2.17, 2.26, 2.30, 2.43 (s, p-Me, 12H),
4.20, 4.93 (c, PCH2, 4H), 6.0–7.7 (m, Ph, 34H). 31P{1H} NMR
2
2
(CDCl3): δ 8.90 (1JPPt = 3070 Hz, JPPt = 50 Hz, JPPЈ = 25 Hz),
26.8 (1JPЈPt = 2272 Hz, JPЈPt = 450 Hz, JPЈP = 25 Hz), Ϫ143.6
(1JPF = 707 Hz). Anal. calc. for C76H74N4P4F12Pt2: C, 51.13; H,
4.18; N, 3.14. Found: C, 52.10; H, 4.43; N, 2.99%.
2
2
Preparation of [Pd(1,8-dpmn)(XylNC)2](PF6)2 3a. To a solu-
tion of PdCl2(1,8-dpmn)ؒ1.5CH2Cl2 (100 mg, 0.12 mmol) in
CH2Cl2 (10 mL), XylNC (33 mg, 0.25 mmol) in CH2Cl2 (10 mL)
and NH4PF6 (98 mg, 0.60 mmol) in acetone (10 mL) was added
at room temperature. After stirring for 2 h, the solvent was
removed to dryness and the residue was extracted with CH2Cl2.
Recystallization from CH2Cl2 and diethyl ether gave pale yellow
crystals of 3a (137 mg, 87%) (contained CH2Cl2 as a solvated
Preparation of [Pd2(1,8-dpmn)2(MesNC)2](PF6)2 8b. To a
solution of 4b (86 mg, 0.06 mmol) in acetone (10 mL) was
added 1,8-dpmn (72 mg, 0.13 mmol) at room temperature.
After stirring for 2 h, the solvent was removed in vacuo and the
residue was extracted with acetone. Reddish orange complex 8b
(30 mg, 55%) was isolated by recrystallization from acetone–
diethyl ether. IR (Nujol): 2133 (N᎐C), 838 (PF ) cmϪ1. UV-vis
᎐
᎐
6
1
(CH2Cl2): λmax 460 nm. H NMR (CDCl3): δ 1.72 (s, o-Me,
Ϫ 1
1H
12H), 2.44 (s, p-Me, 6H), 4.20, 3.8–5.9 (c, PCH2, 8H), 6.6–8.1
᎐
molecule). IR (Nujol): 2213 (N᎐C), 835 (PF ) cm
.
᎐
6
NMR(CD3COCD3): δ 1.97 (s, o-Me, 12H), 4.60 (center of an
AB quartet, JHH = 10.0 Hz, 4H, CH2), 5.27 (s, CH2Cl2), 5.6–8.2.
31P NMR (CDCl3): δ 30.1 (s), Ϫ143.4 (sep., JPF = 707 Hz). Anal.
Calc. for C54H48N2P4F12Pdؒ1.5CH2Cl2: C, 50.86; H, 3.92; N,
2.13. Found: C, 50.44; H, 3.65; N, 1.99%.
(m, Ph, 56H). 31P{1H} NMR (CDCl3): δ 22.16 (2JP1P2 = Ϫ75 Hz,
3
2JP1P2Ј = 60 Hz, JP1P1Ј = 264 Hz), 9.09 (1JP2P1 = Ϫ75 Hz,
3
3JP2P2Ј = 17 Hz, JP2P1Ј = 60 Hz), Ϫ143.6 (1JPF = 707 Hz). Anal.
calc. for C92H82N2P6F12Pd2: C, 59.98; H, 4.49; N, 1.52. Found:
C, 59.65; H, 4.18; N, 1.43%.
Preparation of [Pd2(1,8-dpmn)(XylNC)4](PF6)2 6a. To a solu-
tion of [Pd2(XylNC)6](PF6)2 (100 mg, 0.08 mmol) in CH2Cl2
(10 mL) was added 1,8-dpmn (43.6 mg, 0.08 mmol) in CH2Cl2
(5 mL) at room temperature. After stirring for 2 h, the solvent
was removed to dryness and the residue was extracted with
benzene. Recystallization of the residue from CH2Cl2 and
diethyl ether gave yellow crystals of 6a (71 mg, 57%) (contained
CH2Cl2 as a solvated molecule). IR (Nujol): 2187 (w), 2160 (st.)
Preparation of [Pd2(1,8-dpmn)2(XylNC)2](PF6)2 8a. Reddish
orange complex 8a (55%) was prepared from the reaction of
[Pd2(XylNC)6](PF6)2 with 1,8-dpmn according to a similar
Ϫ1
᎐
procedure to 8b. IR (Nujol): 2132 (N᎐C), 841 (PF ) cm
.
᎐
6
UV-vis (CH2Cl2): λmax 463 nm. 1H NMR (CD3COCD3): δ 1.79
(s, o-Me, 12H), 3.74–5.90 (b, CH2, 8H), 6.2–8.0. 31P{1H} NMR
(CD3COCD3): δ ca. 19.0 (c), ca. 9.0 (c), Ϫ144.4 (sep. 1JPF = 710
Hz). Anal. calc. for C90H78N2P6F12Pd2ؒ0.5CH2Cl2: C, 58.54; H,
4.29; N, 1.15. Found: C, 58.68; H, 4.29; N, 1.31%.
(N᎐C), 837 (PF ) cmϪ 1. UV-vis (CH2Cl2): λmax 385 nm. 1H
᎐
᎐
6
NMR (CD3COCD3): δ 2.11 (s, o-Me, 6H), 2.21 (s, o-Me, 6H),
2.30 (s, o-Me, 6H), 2.38 (s, Me, 6H), ca. 4.1, ca. 4.8, ca. 5.2, ca.
5.5 (b, CH2, 1H), 6.8–7.8. 31P{1H} NMR (CD3COCD3): δ 21.3
(d, JPPЈ = 54.5 Hz), 13.4 (d, JPPЈ = 54.5 Hz), Ϫ143.4 (sep.,
1JPF = 710 Hz). Anal. calc. for C72H66N4P4F12Pd2ؒ0.5CH2Cl2: C,
54.61; H, 4.24; N, 3.51. Found: C, 54.35; H, 4.21; N, 3.53%.
Preparation of [Pt2(1,8-dpmn)2(XylNC)2](PF6)2 9a. To a solu-
tion of 5a (50 mg, 0.034 mmol) in acetone (10 mL) was added
1,8-dpmn (37 mg, 0.07 mmol) at room temperature. After
stirring for 2 h, the solvent was removed in vacuo and the
residue was extracted with acetone. Recrystallization from
acetone–diethyl ether gave yellow crystals of 9a (17 mg, 25%).
2
2
IR (Nujol): 2152 (N᎐C), 841 (PF ) cmϪ1. UV-vis (CH2Cl2): λmax
᎐
Preparation of [Pd2(1,8-dpmn)(MesNC)4](PF6)2 6b. Yellow
crystals (56%) of 6b, recrystallized from acetone and diethyl
ether, were obtained from [Pd2(MesNC)6](PF6)2 and 1,8-dpmn,
according to a procedure similar to that for 6a. IR (Nujol): 2189
᎐
6
1
461 nm. H NMR (CD3COCD3): δ 1.80 (s, o-Me, 12H), 4.2–
5.90 (b, CH2, 8H), 6.2–8.0. Anal. calc. for C90H78N2P6F12Pt2: C,
54.28; H, 3.95; N, 1.41. Found: C, 54.58; H, 4.00; N, 1.66%.
(w), 2162 (st.) (N᎐C), 837 (PF ) cmϪ1. UV-vis. (CH2Cl2): λ 385
᎐
᎐
6
1
nm. H NMR (CD3COCD3): δ 2.02 (s, Me, 3H), 2.08 (s, Me,
Preparation of [Pt2(1,8-dpmn)2(MesNC)2](PF6)2 9b. Pale
yellow crystals (49%) of 9a recrystallized from acetone and
diethyl ether, were obtained from [Pd2(MesNC)6](PF6)2 and 1,8-
6H), 2.15 (s, Me, 6H), 2.22 (s, Me, 9H), 2.3 (s, Me, 12H),
3.88–5.15 (m, CH2, 4H), 5.6–8.2. 31P{1H} NMR (CDCl3): δ 21.2
2
2
(d, JPPЈ = 54.5 Hz), 12.4 (d, JPPЈ = 54.5 Hz), Ϫ143.4 (sep.,
2JPF = 710 Hz). Anal. calc. for C76H74N4P4F12Pd2ؒ(CH3)2CO: C,
56.95; H, 4.84; N, 3.36. Found: C, 57.09; H, 4.81; N, 3.34%.
dpmn, according to a similar procedure to 9b. IR (Nujol): 2154
1
(N᎐C), 837 (PF ) cmϪ1. UV-vis (CH2Cl2): λ 463 nm. H NMR
᎐
᎐
6
(CD3COCD3): δ 1.77 (s, o-Me, 12H), 2.86 (s, p-Me, 6H), 4.2–
5.90 (b, CH2, 8H), 6.2–8.0. Anal. calc. for C92H82N2P6F12Pt2: C,
54.71; H, 4.09; N, 1.39. Found: C, 54.38; H, 4.20; N, 1.55%.
Preparation of [Pt2(1,8-dpmn)(XylNC)4](PF6)2 7a. 1,8-Dpmn
(20 mg, 0.038 mmol) was added to a solution of [Pt2(XylNC)6]-
(PF6)2 (50 mg, 0.034 mmol) in acetone (10 mL mL) at room
temperature and stirred for 2 h. The solvent was concentrated
to ca. 3 mL and diethyl ether was extracted with benzene.
Recrystallization of the residue from acetone and diethyl ether
gave pale yellow crystals of 7a (38 mg, 65%). IR (Nujol): 2202
Preparation
of
[{Pd(1,8-dpmn)(XylNC)2)}{HN(CH2)2-
(CMe2)2CO}2](PF6)4 10a. To a solution of [Pd2Cl2(XylNC)4]
(48 mg, 0.059 mmol) in acetone (10 mL) was added 1,8-dpmn
(72 mg, 0.13 mmol) and NH4PF6 (100 mg, 0.61 mmol) at room
temperature and the mixture was stirred for 24 h. After the
solvent was removed in vacuo, the residue was extracted with
CH2Cl2. Recrystallization from CH2Cl2 and diethyl ether gave
(w), 2164 (st) (N᎐C), 835 (PF ) cmϪ1. 1H NMR (CD3COCD3):
᎐
᎐
6
δ 2.13 (s, o-Me, 6H), 2.22 (s, o-Me, 6H), 2.24 (s, o-Me, 6H), 2.37
J. Chem. Soc., Dalton Trans., 2001, 1773–1781
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J. Chem. Soc., Dalton Trans., 2001, 1773–1781

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yellow crystals (135 mg, 64.1%) of 10a. IR (Nujol): 3198, 3135
See http://www.rsc.org/suppdata/dt/b1/b100860i/ for crystal-
lographic data for 6bؒ(CH3)2CO (157470) and 7b (157471) in
1
(N–H), 2218 (N᎐C), 1725 (C᎐O), 847 (PF ) cmϪ1. H NMR
᎐
᎐
᎐
6
(CDCl3): δ 1.69 (s, Me, 24H), 1.99 (s, o-Me, 12H), 2.87 (s, CH2,
8H), 4.63, 5.86 (c, PCH2, 4H), 6.7–8.2 (m, Ph, 32H). 31P NMR
(CDCl3): δ 30.3 (s), Ϫ143.1 (sep., PF6). Anal. calc. for C72H84-
N4O2P6F24Pd: C, 48.43; H, 4.74; N, 3.14. Found: C, 48.11; H,
4.55; N, 2.97%.
CIF or other electronic format.
Acknowledgements
This work was partially supported by a Grant-in-Aid for
Each cationic compound, [Pd(XylNC)2(1,8-dpmn)](PF6)2
and [HN(CH2)2(CMe2)2CO](PF6) can be separately isolated by
several recrystallizations.
Scientific Research from the Ministry of Education of Japan.
References
Photochemical reaction of [Pd2(1,8-dpmn)2(XylNC)2](PF6)2 8a
in CH2Cl2
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J. Organomet. Chem., 1992, 440, 1.
6 T. Tanase, H. Ukaji, Y. Kudo, M. Ohno, K. Kobayashi and
Y. Yamamoto, Organometallics, 1994, 13, 1374.
7 T. Tanase, T. Fukushima, T. Nomura, Y. Yamamoto and
K. Kobayashji, Inorg. Chem., 1994, 33, 32.
8 Y. Yamamoto and H. Yamazaki, Organometallics, 1993, 12,
933.
A solution of 8a (50 mg, 0.028 mmol) in CH2Cl2 (10 mL) was
irradiated with sunlight. After 3 h, the solvent was removed and
the residue was crystallized from CH2Cl2 and diethyl ether to
give yellow crystals of [PdCl(1,8-dpmn)(XylNC)](PF6) (45 mg,
Ϫ1
᎐
85%). IR (Nujol): 2001 (N᎐C), 845 (PF ) cm
.
1H NMR
᎐
6
(CDCl3): δ 1.83 (s, o-Me, 6H), 3.82, 5.40 (c, PCH2, 4H), 6.2–8.0
(m, Ph, 28H). 31P NMR (CDCl3): δ 32.1 (d, JPP = 35.4 Hz), 32.6
(d, JPP = 35.4 Hz), Ϫ143.1 (sep., JPF = 710 Hz, PF6). Anal. calc.
for C45H39NClP3F6Pd: C, 57.34; H, 4.17; N, 1.49. Found: C,
57.26; H, 3.95; N, 1.35%.
9 T. Tanase, K. Kawahara, H. Ukaji, K. Kobayashi, H. Yamazaki and
Y. Yamamoto, Inorg. Chem., 1993, 32, 3682.
Data collection
10 Y. Yamamoto, T. Tanase, I. Mori and Y. Nakamura, J. Chem. Soc.
Dalton Trans., 1994, 3191.
11 Y. Yamamoto and H. Yamazaki, Inorg. Chem., 1986, 25, 3327.
12 T. Tanase and Y. Yamamoto, Trends Organomet. Chem., 1999, 35
and references therein.
13 R.-X. Li, N.-B. Wong, X.-J. Li, T. C. W. Mak, Q.-C. Yang and K.-C.
Tin, J. Organomet. Chem., 1998, 571, 223.
14 P. Dierkes and P. W. N. M. van Leeuwen, J. Chem. Soc., Dalton
Trans., 1999, 1519.
Complexes, 1ؒCH2Cl2, 2ؒCH2Cl2 6bؒ(CH3)2CO, 7b, 8bؒ2(CH3)2-
CO and 10a, were recrystallized from CH2Cl2–diethyl ether.
Cell constants were determined from 20–25 reflections on a
Rigaku four-circle automated diffractometer AFC5S. The
crystal parameters along with data collections are summarized
in Table 5. Data collection was carried out by a Rigaku AFC5S
refractometer at 27 ЊC. Intensities were measured by the
2θ–ω scan method using Mo-Kα radiation (λ = 0.71069 Å).
Throughout the data collection the intensities of three standard
reflections were measured every 200 reflections as a check of the
stability of the crystals and no decay was observed. Intensities
were corrected for Lorentz and polarization effects. The absorp-
tion correction was made with the ψ scan method. Atomic
scattering factors were taken from Cromer and Waber, the usual
15 Y. Yamamoto and H. Yamazaki, Bull. Chem. Soc. Jpn., 1985, 58,
1848.
16 D. J. Doonan, A. L. Balch, S. Z. Goldberg, R. Eisenberg and J. S.
Miller, J. Am. Chem. Soc., 1975, 15, 1961.
17 S. Z. Goldberg and R. Eisenberg, Inorg. Chem., 1976, 16, 536.
18 T. D. Miller, M. A. S. Clair, M. K. Reinking and C. P. Kubiak,
Organometallics, 1983, 2, 767.
19 N. M. Ruthergord, M. M. Olmstead and A. L. Balch, Inorg. Chem.,
1977, 23, 324.
20 (a) Y. Yamamoto, K. Takahashi, K. Matsuda and H. Yamazaki,
J. Chem. Soc., Dalton Trans., 1987, 1833; (b) Y. Yamamoto,
K. Takahashi and H. Yamazaki, Chem. Lett., 1985, 201.
21 T. Tanase, J. Matsuo, T. Onaka, R. A. Begum, M. Hamaguchi,
S. Yano and Y. Yamamoto, J. Organomet. Chem., 1999, 592,
103.
tabulation.26 Anomalous dispersion effects were included
27
in Fcalc
;
the values of ∆fЈ and ∆fЈЈ were those of Creagh and
McAuley.28 All calculations were performed using the
TEXSAN crystallographic software package.29
Determination of the structures. All structures except
1ؒCH2Cl2, 2ؒCH2Cl2 and 8bؒ2(CH3)2CO (solved by Direct
methods) were solved by Patterson methods (DIRDIF92,
PATTY).30 The positions of all nonhydrogen atoms except
nonhydrogen atoms from the CH2Cl2 solvent for 1ؒCH2Cl2 and
six F atoms for 8bؒ2(CH3)2CO, were refined with anisotropic
thermal parameters by using full-matrix least-squares methods.
The positions of all nonhydrogen atoms except the Pt, Cl and
P atoms for 2, and the Pt and P atoms for 7b were refined
with isotropic thermal parameters by using full-matrix least-
squares methods. The positions of all nonhydrogen atoms of
6bؒ(CH3)2CO were refined with anisotropic thermal parameters
by using full-matrix least-squares methods. The positions of the
Pd, P and two N atoms for 10a were refined anisotropically and
other nonhydrogen atoms were refined isotropically. All
hydrogen atoms were calculated at the ideal positions with the
C–H distance of 0.95 Å and not refined.
22 Y. Yamamoto and F. Arima, J. Chem. Soc. Dalton Trans., 1996,
1815.
23 H. M. Walborsky and G. E. Niznik, J. Org. Chem., 1972, 37,
187.
24 (a) T. Kamada, Y. Gama and N. Wasada, Bull. Chem. Soc. Jpn.,
1989, 62, 3024; (b) V. Boekelheide and G. K. Vick, J. Am. Chem.
Soc., 1956, 78, 653.
25 Y. Yamamoto and H. Yamazaki, Bull. Chem. Soc. Jpn., 1985, 58,
1843.
26 D. T. Cromer and J. T. Waber, International Tables for X-Ray
Crystallography, Kynoch Press, Birmingham, 1974, Table 2.2A.
27 J. A. Ibers and W. C. Hamilton, Acta Crystallogr., 1964, 17, 781.
28 D. C. Creagh and W. J. McAuley, International Tables for X-Ray
Crystallography, Kluwer, Boston, 1992, vol. C, Table 4.2.6.8,
pp. 200–206.
29 TEXSAN, Crystal Structure Analysis Package, Molecular Structure
Corporation, Houston, TX, 1985 and 1992.
30 P. T. Beurskens, DIRDIF92, Direct Methods for Difference
Structures, an automatic procedure for phase extension and
refinement of difference structure factors, Crystallography
Laboratory, Töernooiveld, Nijmegen, 1992.
CCDC reference numbers 157470, 157471 and 161769–
161772.
J. Chem. Soc., Dalton Trans., 2001, 1773–1781
1781