A metallanaphthalyne complex from zinc reduction of a vinylcarbyne complex

Article abstract of DOI:10.1002/anie.200703289

Cl prevents insertion: The first metallanaphthalyne 2 has been obtained by Zn reduction of Os carbyne complex 1. The key to its isolation was the use of o-chlorophenyl instead of phenyl substituents to avoid formation of a putative hydrido metallanaphthalyne intermediate (supported by DFT calculations), which undergoes migratory insertion of the carbyne into the Os-H bond and rearrangement to give an indenyl complex as the final product. (Chemical Equation Presented).

Full text of DOI:10.1002/anie.200703289

Angewandte
Chemie
DOI: 10.1002/anie.200703289
Metallaarenes
A Metallanaphthalyne Complex from Zinc Reduction of a
Vinylcarbyne Complex**
Guomei He, Jun Zhu, Wai Yiu Hung, Ting Bin Wen, Herman Ho-Yung Sung,
Ian Duncan Williams, Zhenyang Lin,* and Guochen Jia*
Transition metal containing metallaaromatics are a fascinat-
ing class of compounds because they can show properties of
both organometallic compounds and aromatic organic com-
pounds.[1] The most common metallaaromatics are metal-
labenzenes, stable examples of which have been found for
osmium,[2] iridium,[3] platinum,[4] and ruthenium.[5] Other
interesting metallaaromatics and related compounds isolated
in recent years include metallanaphthalene,[6] metallapyry-
lium,[7] metallathiabenzene,[8] metallapyridine,[9] metallaben-
zyne,[10] isometallabenzene,[11] and metallabenzvalene.[12]
Here we report the synthesis and characterization of the
first metallanaphthalyne.
Compared to metallabenzenes, the chemistry of metal-
labenzynes is less developed, partly due to the lack of
convenient methods to construct the metallabenzyne ring. In
a search for new routes to metallabenzynes, we tried to reduce
ꢀ
=
the carbyne complex [OsCl3( CCH CPh2)(PPh3)2] (1) with
zinc.[13] We envisaged that Zn might first reduce the carbyne
Figure 1. Molecular structure of [{h5-C9H6(Ph)}OsCl(PPh3)2] (2).
ꢀ
=
complex to the 16e species [OsCl( CCH CPh2)(PPh3)2],
À
which could undergo C H oxidative addition to give an
osmanaphthalyne. Treatment of 1 with zinc powder in THF
heated at reflux for 1.5 h produced the indenyl complex
[{h5-C9H6(Ph)}OsCl(PPh3)2] (2), along with other unidentified
species. Complex 2 can be isolated in 39% yield from the
reaction. The reaction is cleaner in the presence of PPh3. In
this case, complex 2 can be isolated as a red solid in 71% yield
[Eq. (1)].
À
ligands. The Os C bond lengths (2.174(5)–2.359(5) Š) are
comparable with those of the reported indenyl complex
[Os(h5-C9H7)(NCCH3)(PiPr3)2]OTf (2.184(3)–2.417(3) Š).[15]
The solid-state structure of 2 is supported by the solution
NMR spectroscopic data. In particular, the 31P{1H} NMR
spectrum (in CD2Cl2) displayed two doublets at d = À7.4 and
0.3ppm with a coupling constant of 17.1 Hz. Observation of
two 31P signals for 2 is expected, because the Os center is
1
chiral. The H spectrum (in CD2Cl2) showed signals of the
h5-indenyl ring at d = 3.63 and 5.41 ppm. The 13C{1H} spec-
trum (in CD2Cl2) displayed the signals of the h5-indenyl ring
at d = 79.6, 84.2, 108.5, 108.6, and 110.6 ppm.
A plausible mechanism for the formation of 2 is shown in
Scheme 1. Reduction of 1 with Zn may initially give 16e
The structure of 2 was determined by single-crystal X-ray
diffraction[14] (Figure 1), which clearly revealed that the
complex contains an indenyl, a chlorido, and two PPh3
[*] G. He, J. Zhu, Dr. W. Y. Hung, Dr. T. B. Wen, Dr. H.-Y. Sung,
Prof. Dr. I. D. Williams, Prof. Dr. Z. Lin, Prof. Dr. G. Jia
Department of Chemistry
The Hong Kong University of Science and Technology
Clear Water Bay, Kowloon (Hong Kong)
Fax: (+852)2358-7361
E-mail: chzlin@ust.hk
chjiag@ust.hk
[**] This work was supported by the Hong Kong Research Grant Council
(601007, 602304).
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Scheme 1. Proposed mechanism for the formation of 2.
Angew. Chem. Int. Ed. 2007, 46, 9065 –9068
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
9065
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

Communications
carbyne complex A, which could undergo cyclometalation to
give hydrido osmanaphthalyne intermediate B. Migratory
À
insertion of the carbyne into the Os H bond of B gives
osmanaphthalene C, which rearranges to the final product 2.
This is reasonable since formation of Cp complexes from
metallabenzenes is known.[3e,h]
Although the reaction intermediates shown in Scheme 1
were not identified, DFT calculations provide support for the
proposed mechanism. Figure 2 shows the potential-energy
ꢀ
=
profiles for the transformation of [OsCl( CCH CHPh)-
(PH3)2] (A’, a model complex of A) to [(h5-C9H7)OsCl(PH3)2]
(2’, a model complex of 2).
The DFT calculations indicate that the pathway leading to
formation of indenyl complex 2’ is both kinetically and
thermodynamically feasible. The important step for the
reaction is isomerization of A’ to A’’, a square-pyramidal
complex with two cis PH3 ligands. Once A’’ is formed, it
À
undergoes C H activation to give hydrido osmanaphthalyne
complex B’ with almost no barrier. Complex 2’ is formed from
C’, an osmanaphthalene intermediate generated by migratory
insertion of B’, with a significant barrier.
Scheme 2. Preparation of 6 and 7.
Treatment of 5 with zinc powder in
the presence of PPh3 in THF produced
the green osmanaphthalyne complex 6
and the red indenyl complex 7, owing
to competitive oxidative addition of
À
À
C Cl and C H bonds, respectively.
Complexes 6 and 7 can be separated
by chromatography. The structure of 7
can be assigned easily, as it has NMR
data similar to those of 2, which has
been structurally characterized by
single-crystal X-ray diffraction.
The most notable product formed
in the reaction is compound 6. As
confirmed by single-crystal X-ray dif-
fraction analysis, it contains an essen-
tially planar metallanaphthalyne unit
(Figure 3). The maximum deviation
from the least-squares plane of the
metallacycle
(Os1,
C1–C5)
is
Figure 2. Energy profile for the formation of 2’ from A’. The calculated relative free energies and
0.034(3) Š for C5, and that for the
whole metallanaphthalyne system
(Os1, C1–C9) is À0.081(2) Š for Os1.
reaction energies (in parentheses) are given in kcalmolÀ1
.
À
The DFTresults show that formation of osmanaphthalyne
The Os C1 bond length (1.732(4) Š) is within the range of
À
ꢀ
complex B via C H activation of A is energetically feasible.
those observed for typical Os C bonds (1.69–1.79 Š)[16,17] and
The problem is that it readily undergoes migratory insertion
of the hydride ligand to finally give indenyl complex 2. On the
basis of the DFT results, we deduce that if the hydride ligand
is replaced by a chloride ligand, the migratory insertion
reaction should be discouraged and an osmanaphthalyne
complex could be isolated.
is significantly smaller than those found for typical vinylidene
[16,18]
= =
À
complexes Os C CRR’ (1.78–1.90 Š).
length (2.127(3) Š) is within the range of those observed for
typical Os C(aryl) bonds (1.98–2.28 Š)
end of typical Os C(carbene) bonds (1.78–2.14 Š).
Despite the large difference in the Os C bond lengths, no
simple C C bond-distance alternation was observed for the
metallacycle, as would be implied from the canonical form
The Os C5 bond
[16,19]
À
and at the high
[16,20]
=
À
À
This theoretical prediction was confirmed by reaction of
ꢀ
=
[OsCl3{ CCH C(2-ClC6H4)2}(PPh3)2] (5) with Zn. The pre-
viously unknown complex 5 was obtained as a mixture of
meridional and facial isomers in an approximate ratio of 4:3
À
À
drawn in Scheme 2. The Os C and C C bond lengths within
the six-membered ring, together with its planar nature,
indicate that the metallacycle has a more delocalized
nature. The Os1-C1-C2 angle of 155.0(3)8 is similar to those
observed for osmabenzynes and is significantly smaller than
ꢀ
from a one-pot reaction of [OsCl2(PPh3)3] (3) with HC
CC(OH)(2-ClC6H4)2 (4) in the presence of HCl in CH2Cl2
(Scheme 2).
9066 www.angewandte.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 9065 –9068
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

Angewandte
Chemie
(1 mL). Addition of hexane (15 mL) to the solution gave a brownish
green precipitate, which was collected by filtration, washed with
hexane (2 ” 2 mL) and diethyl ether (2 ” 1 mL), and dried under
vacuum to give 0.165 g of crude product containing predominantly 6
and a small amount of 7. To separate 6 and 7, the brownish green solid
was dissolved in benzene (3mL) and loaded onto a silica gel column.
The column was eluted with benzene and CH2Cl2 sequentially to give
red 7 and green 6, respectively, which were dried under vacuum.
Yield: 6, 88 mg, 25%; 7, 15 mg, 4.3%. Selected spectroscopic data of
6: 31P{1H} NMR (121.5 MHz, C6D6): d = À0.6 (d, J(PP) = 474.0 Hz),
À3.3 ppm (d, J(PP) = 474.0 Hz). 1H NMR (300.13 MHz, C6D6): d =
ꢀ
=
3.77 (s, 1H; Os CCH ), 5.99 (t, J(HH) = 7.5 Hz, 1H; Ph), 6.13(d,
J(HH) = 6.6 Hz, 1H; Ph), 6.22 (t, J(HH) = 7.4 Hz, 1H; Ph), 8.86 (d,
J(HH) = 8.3Hz, 1H; Ph), 6.46–7.75 ppm (m, 34H; other aromatic
protons); 13C{1H} NMR (75.5 MHz, C6D6): d = 277.9 (t, J(PC) =
ꢀ
ꢀ
=
11.7 Hz; Os C), 175.4 (s; Os CCH C), 164.4 (t, J(PC) = 6.7 Hz;
À
ꢀ
=
Os C), 119.1 (s, Os CCH ), 121.3–142.8 ppm (m, other aromatic
carbon atoms); elemental analysis (%) calcd for C51H39Cl3P2Os:
C 60.63, H 3.89; found: C 60.75, H 4.06; TOF LD + MS: m/z 973.2
[MÀCl]+, 939.2 [MÀ2Cl]+, 826.2 [MÀ2ClÀPhCl]+. Selected spectro-
scopic data of 7: 31P{1H} NMR (121.5 MHz, CD2Cl2): d = À6.9 (d,
J(PP) = 16.9 Hz), À0.5 ppm (d, J(PP) = 16.9 Hz); 1H NMR
(300.13 MHz, C6D6): d = 3.38 (brs, 1H; h5-C9H5Cl(2-ClPh)), 5.18 (d,
J(HH) = 5.3Hz, 1H; h5-C9H5Cl(2-ClPh)), 5.32 (d, J(HH) = 8.3Hz,
1H; h5-C9H5Cl(2-ClPh)), 5.91 (t, J(HH) = 7.8 Hz, 1H; h5-C9H5Cl(2-
ClPh)), 6.25–7.40 (m, 34H; Ph, PPh3, h5-C9H5Cl(2-ClPh)), 9.51 ppm
(dd, J(HH) = 7.8, 1.5 Hz, 1H; h5-C9H5Cl(2-ClPh)); 13C{1H} NMR
(75.5 MHz, CD2Cl2): d = 125.4–140.4 (m; Ph, PPh3, h5-C9H5Cl(2-
ClPh)), 120.8 (s; h5-C9H5Cl(2-ClPh)), 90.8 pm (s, h5-C9H5Cl(2-
ClPh)); elemental analysis (%) calcd for C51H39Cl3P2Os: C 60.63, H
3.89; found: C 61.00, H 4.16.
Figure 3. Molecular structure of 6. Selected bond lengths [Š] and
À
À
À
angles [8]: Os1 P1 2.4193(9), Os1 P2 2.4088(9), Os1 Cl1 2.4568(9),
À
À
À
À
Os1 Cl2 2.4766(9), Os1 C1 1.732(4), Os1 C5 2.127(3), C1 C2
À
À
À
À
1.375(5), C2 C3 1.368(5), C3 C4 1.457(5), C4 C5 1.432(5), C5 C6
À
À
À
À
1.396(5), C6 C7 1.378(5), C7 C8 1.374(5), C8 C9 1.363(5), C9 C4
1.425(5); P1-Os1-P2 175.35(3), C1-Os1-C5 79.84(15), Os1-C1-C2
155.0(3), C1-C2-C3 112.6(3), C2-C3-C4 123.4(3), C3-C4-C5 124.0(3),
C4-C5-Os1 125.0(3), C4-C5-C6 114.5(3), C5-C6-C7 123.9(4), C6-C7-C8
121.3(4), C7-C8-C9 117.9(4), C8-C9-C4 122.1(4), C9-C4-C5 120.1(4).
2 and 5: See the Supporting Information for details.
The DFT computational details are the same as those described
in ref. [22].
that expected for a carbyne or vinylidene complex owing to
the constraint of the six-membered ring. Consistent with the
solid-state structure, the 13C{1H} NMR spectrum of 6 dis-
Received: July 23, 2007
Published online: October 24, 2007
ꢀ
À
played signals for Os C and Os C5 at d = 277.9 and
164.4 ppm, respectively. The 31P{1H} NMR spectrum showed
two signals for the two PPh3 ligands, that is, the two P atoms in
6 are magnetically inequivalent due to slow rotation of the
ortho-chlorophenyl group.
Keywords: carbyne ligands · cyclization · indenyl ligands ·
.
metallacycles · osmium
Since the structure of 6 is closely related to that of 1,2-
naphthalyne, it can be regarded as a metallanaphthalyne. 1,2-
Naphthalynes[21] generated in situ have often been used in
organic synthesis.[21a] However, they have low thermal stabil-
ity and have only been detected in argon matrix at low
temperature.[21b,c]
[1] a) J. R. Bleeke, Chem. Rev. 2001, 101, 1205; b) C. W. Landorf,
M. M. Haley, Angew. Chem. 2006, 118, 4018; Angew. Chem. Int.
Ed. 2006, 45, 3914; c) L. J. Wright, Dalton Trans. 2006, 1821.
[2] a) G. P. Elliott, W. R. Roper, J. M. Waters, J. Chem. Soc. Chem.
Commun. 1982, 811; b) C. E. F. Rickard, W. R. Roper, S. D.
Woodgate, L. J. Wright, Angew. Chem. 2000, 112, 766; Angew.
Chem. Int. Ed. 2000, 39, 750; c) C. E. F. Rickard, W. R. Roper,
S. D. Woodgate, L. J. Wright, J. Organomet. Chem. 2001, 623,
109; d) H. Xia, G. He, H. Zhang, T. B. Wen, H. H. Y. Sung, I. D.
Williams, G. Jia, J. Am. Chem. Soc. 2004, 126, 6862; e) G. R.
Clark, P. M. Johns, W. R. Roper, L. J. Wright, Organometallics
2006, 25, 1771.
In summary, we have synthesized the first well-charac-
terized example of a metallanaphthalyne 6 by Zn reduction of
ꢀ
=
[OsCl3{ CCH C(2-ClC6H4)2}(PPh3)2]. In addition, we also
found that indenyl complexes can be formed from hydrido
metallanaphthalynes, and this suggests that metallabenzynes
could be important intermediates in organometallic reactions.
Preparation of other metallanaphthalynes is now underway.
[3] For example: a) M. Paneque, M. L. Poveda, N. Rendón, E.
lvarez, E. Carmona, Eur. J. Inorg. Chem. 2007, 2711; b) G. R.
Clark, G. L. Lu, W. R. Roper, L. J. Wright, Organometallics
2007, 26, 2167; c) E. lvarez, M. Paneque, M. L. Poveda, N.
Rendón, Angew. Chem. 2006, 118, 488; Angew. Chem. Int. Ed.
2006, 45, 474; d) K. Ilg, M. Paneque, M. L. Poveda, N. Rendón,
L. L. Santos, E. Carmona, K. Mereiter, Organometallics 2006, 25,
2230; e) H. P. Wu, T. J. R. Weakley, M. M. Haley, Chem. Eur. J.
2005, 11, 1191; f) C. S. Chin, H. Lee, M. S. Eum, Organometallics
2005, 24, 4849; g) C. S. Chin, H. Lee, Chem. Eur. J. 2004, 10,
4518; h) R. D. Gilbertson, T. L. S. Lau, S. Lanza, H. P. Wu,
T. J. R. Weakley, M. M. Haley, Organometallics 2003, 22, 3279;
i) H. P. Wu, S. Lanza, T. J. R. Weakley, M. M. Haley, Organo-
Experimental Section
6 and 7: A mixture of 5 (0.380 g, 0.35 mmol), zinc powder (0.480 g,
7.34 mmol), and triphenylphosphine (91.7 mg, 0.35 mmol) in THF
(30 mL) was refluxed for 25 min. The solvent was removed com-
pletely under vacuum and the residue was extracted with benzene
(13mL) and filtered. The extract was concentrated to about 5 mL.
Diethyl ether (15 mL) was added slowly to give an orange precipitate,
which was removed by filtration, and the solvent of the brown filtrate
was removed under vacuum and the residue dissolved in CH2Cl2
Angew. Chem. Int. Ed. 2007, 46, 9065 –9068
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org 9067
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

Communications
metallics 2002, 21, 2824; j) R. D. Gilbertson, T. J. R. Weakley,
[13] T. B. Wen, Z. Y. Zhou, M. F. Lo, I. D. Williams, G. Jia, Organo-
metallics 2003, 22, 5217.
[14] See the Supporting Information for single-crystal X-ray diffrac-
tion data.
[15] M. A. Esteruelas, A. M. López, E. Oꢀate, E. Royo, Organo-
metallics 2005, 24, 5780.
[16] Based on a search of the Cambridge Structural Database, CSD
M. M. Haley, J. Am. Chem. Soc. 1999, 121, 2597; k) J. R. Bleeke,
R. Behm, J. Am. Chem. Soc. 1997, 119, 8503; l) J. R. Bleeke, R.
Behm, Y. F. Xie, M. Y. Chiang, K. D. Robinson, A. M. Beatty,
Organometallics 1997, 16, 606; m) J. R. Bleeke, Y. F. Xie, L. Bass,
M. Y. Chiang, J. Am. Chem. Soc. 1991, 113, 4703; n) J. R. Bleeke,
Y. F. Xie, W. J. Peng, M. Chiang, J. Am. Chem. Soc. 1989, 111,
4118.
version 5.27 (August 2006).
ꢀ
=
[4] a) V. Jacob, T. J. R. Weakley, M. M. Haley, Angew. Chem. 2002,
114, 3620; Angew. Chem. Int. Ed. 2002, 41, 3 470; b) C. W.
Landorf, V. Jacob, T. J. R. Weakley, M. M. Haley, Organometal-
lics 2004, 23, 1174.
[5] a) H. Zhang, H. Xia, G. He, T. B. Wen, L. Gong, G. Jia, Angew.
Chem. 2006, 118, 2986; Angew. Chem. Int. Ed. 2006, 45, 2920;
b) H. Zhang, L. Feng, L. Gong, L. Wu, G. He, T. Wen, F. Yang, H.
Xia, Organometallics 2007, 26, 2705.
[6] a) M. Paneque, C. M. Posadas, M. L. Poveda, N. Rendón, V.
Salazar, E. Oꢀate, K. Mereiter, J. Am. Chem. Soc. 2003, 125,
9898; b) M. Paneque, C. M. Posadas, M. L. Poveda, N. Rendón,
L. L. Santos, E. lvarez, V. Salazar, K. Mereiter, E. Oꢀate,
Organometallics 2007, 26, 3403.
[17] Recent examples: a) [Os( CCH CPh)H(OAc)(PiPr3)2]BF4
(1.740(4) Š): T. Balaꢀo, R. Castarienas, M. A. Esteruelas, E.
ꢀ
=
Oꢀate, Organometallics 2007, 26, 2037; b) [Os( CCH CPh)H-
(OPh)(MeCN)(PiPr3)2]BF4 (1.740(5) Š): T. Balaꢀo, R. Castar-
ienas, M. A. Esteruelas, E. Oꢀate, J. Am. Chem. Soc. 2007,
129, 8850; c) [Os( CC6H4CHMe2)H2{N(SiMe2CH2PtBu2)2}]
(1.746(3) Š): J. H. Lee, M. Pink, K. G. Caulton, Organometallics
2006, 25, 802; d) [OsH( CCH CPh2)(H2O)2(PiPr3)2](BF4)2
(1.733(6) Š): T. Bolaꢀo, R. Castarlenas, M. A. Esteruelas, F. J.
Modrego, E. Oꢀate, J. Am. Chem. Soc. 2005, 127, 11184.
ꢀ
ꢀ
=
= =
=
[18] For example: a) [CpOsCl( C CHPh)(PiPr2{C(CH3) CH2})]
(1.817(5) Š): M. Baya, M. L. Buil, M. A. Esteruelas, E. Oꢀate,
Organometallics 2005, 24, 2030; b) [OsCl2( C CHPh)(PPh3)2]
= =
[7] a) J. R. Bleeke, J. M. B. Blanchard, J. Am. Chem. Soc. 1997, 119,
5443; b) J. R. Bleeke, J. M. B. Blanchard, E. Donnay, Organo-
metallics 2001, 20, 324.
(1.796(3) Š): T. B. Wen, W. Y. Hung, Z. Y. Zhou, M. F. Lo, I. D.
Williams, G. Jia, Eur. J. Inorg. Chem. 2004, 2837.
=
[19] For
example:
a) [Os(C6H4CPh NH)Cl(CO)(PiPr3)2]
[8] See for example: a) J. Chen, L. M. Daniels, R. J. Angelici, J. Am.
Chem. Soc. 1990, 112, 199; b) R. M. Chin, W. D. Jones, Angew.
Chem. 1992, 104, 340; Angew. Chem. Int. Ed. Engl. 1992, 31, 357;
c) C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, P. Frediani, V.
Herrera, R. A. Sanchez-Delgado, J. Am. Chem. Soc. 1993, 115,
2731; d) J. R. Bleeke, P. V. Hinkle, N. P. Rath, J. Am. Chem. Soc.
1999, 121, 595.
(2.038(2) Š): M. L. Buil, M. A. Esteruelas, E. Goni, M. Olivan,
E. Oꢀate, Organometallics 2006, 25, 3076; b) [OsH(h5-C5H5)-
{C6H4C(O)CH3}(PiPr3)]BF4 (2.016(5) Š): M. A. Esteruelas,
Y. A. Hernꢁndez, A. M. López, M. Olivꢁn, E. Oꢀate, Organo-
=
metallics 2005, 24, 5989; c) [CpOsH(C6H4CPh NH)(PiPr3)]OTf
(2.137(19) Š): M. A. Esteruelas, E. Gutierrez-Pueba, A. M.
López, E. Oꢀate, J. I. Tolosa, Organometallics 2000, 19, 275.
=
[9] K. J. Weller, I. Filippov, P. M. Briggs, D. E. Wigley, Organo-
metallics 1998, 17, 322.
[20] Recent
examples:
a) [Os( CHPh)(MeCN)4(iPr)](OTf)2
(1.926(6) Š): R. Castarlenas, M. A. Esteruelas, E. Oꢀate,
=
b) [HPiPr3][OsCl3{
[10] See, for example: a) T. B. Wen, Z. Y. Zhou, G. Jia, Angew. Chem.
2001, 113, 2005; Angew. Chem. Int. Ed. 2001, 40, 1951; b) G. Jia,
Acc. Chem. Res. 2004, 37, 479; c) T. B. Wen, W. Y. Hung,
H. H. Y. Sung, I. D. Williams, G. Jia, J. Am. Chem. Soc. 2005,
127, 2856; d) W. Y. Hung, J. Zhu, T. B. Wen, K. P. Yu, H. H. Y.
Sung, I. D. Williams, Z. Lin, G. Jia, J. Am. Chem. Soc. 2006, 128,
13742.
Organometallics
C(Ph)CH2Ph}(CO)(PiPr3)2]
2007,
26,
2129;
=
[OsCl{
(1.929(3) Š),
C(Ph)CH2Ph}(CO)(PiPr3)2]BF4 (1.888(3) Š): M. A. Esteruelas,
López, E. Oꢀate, Organometallics 2007, 26, 3260.
[21] See, for example: a) D. Peꢀa, D. Pꢂrez, E. Guitiꢁn, L. Casted, J.
Org. Chem. 2000, 65, 6944; b) T. Sato, H. Niino, A. Yabe, J. Phys.
Chem. A 2001, 105, 7790; c) J. Yu, R. Sumathi, W. H. Green, Jr.,
J. Phys. Chem. A. 2006, 110, 6971.
[11] P. Barrio, M. A. Esteruelas, E. Oꢀate, J. Am. Chem. Soc. 2004,
126, 1946.
[22] J. Zhu, G. Jia, Z. Lin, Organometallics 2007, 26, 1986.
[12] R. D. Gilbertson, T. J. R. Weakley, M. M. Haley, Chem. Eur. J.
2000, 6, 437.
9068 www.angewandte.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 9065 –9068
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&