Electron-poor rhenium allenylidenes and their reactivity toward phosphines: A combined experimental and theoretical study

Article abstract of DOI:10.1021/om200083h

The reaction of 1-(phenyl)-1-(p-nitrophenyl)-2-propyn-1-ol with the Re(I) precursor [(triphos)(CO)₂Re(OTf)] in dichloromethane at 0 °C afforded the cationic allenylidene complex [(triphos)(CO)₂Re{C=C= C(C₆H₅)(p-

Full text of DOI:10.1021/om200083h

Supporting Information
Energy decomposition.
We employed the scheme developed by Ziegler and Rauk in Cs symmetry which allows to separate
the orbital interaction contributions to the bond energy within the irreducible representations A′ and
A′′, corresponding to σ and π interactions. We first reoptimized all complexes in Cs symmetry and
the results of the bond analysis are presented in Table S1 together with the analogous bonding
contributions for the parent diphenyl complex. Table S1 shows small steric energies indicating that
the bonding dissociation energy is mainly due to the orbital interaction. It is worth noting that the
small decrease of the bonding energy upon the insertion of one or two p-nitro groups on the phenyls
comes from the compensation of two opposite effects: an increase of the attractive orbital
interaction and a slightly larger increase of the steric repulsion between the metal fragment and the
allenylidene unit.
Stereoisomers and Rotamers for the α-phosphonioallenyl adducts.
In the α-phosphonioallenyl species, rotation is in principle possible around Re−Cα and Cα−P
bonds: the rotation around Re−Cα leads to three possible relative orientations of the
phosphonioallenyl ligand with (i) the phosphonio unit pointing toward the triphos phenyl groups
(and the allenyl unit toward the carbonyl ligands), (ii) the phosphonio unit pointing toward the
carbonyl ligands (and the allenyl unit toward the triphos phenyl groups), or (iii) the phosphonio and
allenyl moieties lying both in between one CO and one triphos phenyl group, respectively, A, B and
C in Chart S1.
No clear possibility can be envisaged for the rotation around the Cα−P bond, but one of the
substituents has likely to be almost eclipsed with either the Cα=Cβ or the Cα−Re bond, in order to
keep the other two substituents staggered, respectively D and E in Chart S2.
1

These forecasts were checked against a detailed analysis of all the minima obtained from geometry
optimizations of the most plausible orientations of the rotatable bonds of the phosphine addition (as
discussed in the manuscript). Moreover, in order to determine the existence of different rotamers
and estimate the energy barriers involved in their interconversion, we performed an energy scan
around each of the corresponding rotatable bonds and the results are reported in Figures S2 and S3
and discussed in the following. Indeed, for atropoisomerism to be observed, the involved rotamers
have to be separated by sufficiently high barriers both for the clockwise and anticlockwise rotation
of the corresponding dihedral angle. All the scans were performed using the experimental
{C=C=C(Ph)(p-C6H4NO2)} species with the bulkier PMePh2 phosphine, the only one
experimentally showing the presence of different rotamers at low temperature. The scans were
carried out at the PBE/BS1 level of theory and, whenever necessary, the energies corresponding to
minima and transition states were also re-evaluated at the MP2/BS2 level of theory.
The results of the optimizations of the different conformers arising from the rotation around the
Re−Cα bond in the α-phosphonio allenyl species indicate that the most stable conformations show
orientation C, see Chart S1, with the phosphonio and allenyl moieties lying both in between one CO
and one triphos phenyl group, while the lowest conformations showing orientation A are
significantly higher in energy and orientation B was only found (high in energy) for the bulkier
PMePh2 phosphine complex. These results suggest that the stability of the various possible
conformations depends on a subtle balance between steric repulsion and π-stacking among phenyl
rings. Indeed, the most stable conformations with orientation C show one or more tight π-stacking
between the protruding phenyl rings on the triphos ligand and those on the allenyl and/or on the
phosphonium units. Finally, when the rotation around the Cα-P bond is considered, all the
optimized conformers only show orientation D, see Chart S2.
This analysis is confirmed by the energy scans: the scan performed by rotating around the Re-Cα
bond (Fig S2) shows two minima within 2 kcal mol-1 corresponding to orientation C, distorted to
allow the allenylidene terminal p-nitrophenyl to interact with one of the triphos phenyl groups, and
2

a further minimum higher in energy (ca. 7 kcal mol-1) corresponding approximately to conformation
B. These three minima are separated by two low barriers, less than 10 kcal mol-1, too small to
account for any possible atropoisomerism.
The energy scan for the rotation around the Cα-P bond for the experimental phenyl p-nitrophenyl
phosphonio species (see Fig. S3) shows the presence of three minima very close in energy and
separated by energy barriers of, at most, 11 and 8 kcal mol-1, values indicating that no
atropoisomerism can be observed for these rotamers in agreement with the experiment.
Table S1. Bond dissociation energy decomposition (kcal mol-1) calculated at the
PBE/BS4//PBE/BS3 level in Cs symmetry, for the [(triphos)(CO)2Re(C=C=CRR’)]+ allenylidenes
with R = R’ = Ph; R = Ph, R’ = p-C6H4NO2; R = R’ = p-C6H4NO2, and R = H, R’ = p-C6H4NO2.
R, R’
Ph, Ph
E*
EPauli
220
Eelect
-198
-193
ESter
22
Eorb
-109
-113
EA’
-80
-80
EA’’
-29
-33
-87
-86
Ph, p-C6H4NO2
220
27
p-C6H4NO2 , p-
C6H4NO2
-85
-92
213
206
-184
-183
29
23
-114
-115
-79
-78
-35
-37
H, p-C6H4NO2,
Table S2. Breakdown of the contributions from rhenium and allenylidene carbon atoms (at the
PBE/BS4//PBE/BS3 level) to the LUMO of the [(triphos)(CO)2Re(C=C=CRR’)]+ allenylidenes
with R = R’ = Ph; R = Ph, R’ = p-C6H4NO2; R = R’=p-C6H4NO2, and R=H, R’=p-C6H4NO2.
R, R’
M
Cα
Cβ
Cγ
ΜΟ
ε
3

HOMO
LUMO
-7.49
-6.11
33.3
8.4
8.0
21.7
-
-
21.3
-0.39
9.3
26.8
-0.17
-
Ph, Ph
Mulliken Charge
HOMO
0.35
31.2
6.7
0.08
22.9
2.4
-7.72
-6.46
LUMO
18.6
-0.36
9.4
21.7
-0.17
-
Ph, p-C6H4NO2
Mulliken Charge
HOMO
0.37
37.6
7.6
0.09
24.4
3.4
-7.98
-6.79
LUMO
20.8
-0.35
9.4
18.5
-0.17
-
p-C6H4NO2 , p-C6H4NO2
H, p-C6H4NO2,
Mulliken Charge
HOMO
0.39
38.8
9.32
0.09
25.0
3.8
-7.96
-6.73
LUMO
20.6
23.6
Table S3. Energies, enthalpies and free energies for the formation of the adducts of the addition of
PMe3 to the Cγ atom of the considered [(triphos)(CO)2Re(=C=C=CRR’)]+ allenylidenes (R=R’=Ph,
R=Ph, R’=p-C6H4NO2, R=R’=p-C6H4NO2, and R=H, R’=p-C6H4NO2), calculated at the
LMP2/BS2//PBE/BS1 level of theory (kcal mol-1).
R, R’
ꢀEgas
-5.6
ꢀEsol
-3.4
-5.0
-6.2
ꢀHsol
-3.6
-2.7
-4.9
ꢀGsol
11.5
10.9
8.2
R=R’=Ph
R=Ph, R’=p-C6H4NO2
R=R’= p-C6H4NO2
-7.2
-9.8
4

Ar
Ar
PR3
P
P
P
P
P
P
Ar
Ar
R3P
OC
CO
CO
CO
OC
OC
PR3
C
A
B
Ar
Chart S1.
Ar
Possible orientations of the phosphonioallenyl ligand with respect to the
[(triphos)(CO)2Re]+ metal fragment through rotation around the Re−Cα bond in the α-phosphonio
allenyl product.
Re
P
Re
P
R
R
R
R
R
R
D
Chart S2. Possible orientations of the PR3 group with respect to the allenyl unit through rotation
E
around the Cα−P bond in the α-phosphonio allenyl product.
5

Figure S1. Energy scan for the attack of PMe3 to the Cγ atom of the bis-p-nitro-phenyl
allenylidene, using as reaction coordinate the P-Cγ distance.
6

Figura S2. Energy scan for the rotation around Re−Cα bond in the α-phosphonio allenyl product of
the addition of PMePh2 to the asymmetric {C=C=C(Ph)(p-C6H4NO2)} allenylidene. Angle in
degrees, energies in kcal mol-1.
7

Figura S3. Energy scan for the rotation around RCα−P bond in the α-phosphonio allenyl product of
the addition of PMePh2 to the asymmetric {C=C=C(Ph)(p-C6H4NO2)} allenylidene. Angle in
degrees, energies in kcal mol-1.
8

Cartesian coordinates
We report below the cartesian coordinated for all considered nitrosubstituted allenylidenes and
their adducts with PMe3 and PMePh2.
The cartesian coordinates for the unsubstituted [(triphos)(CO)2Re(=C=C=CPh2)]+ allenylidene
complex and all its adducts with PMe3 and PMePh2 can be found in ref. Coletti, C.; Gonsalvi, L.;
Guerriero, A.; Marvelli, L.; Peruzzini, M.; Reginato, G.; Re, N. Organometallics, 2010, 29, 5982 –
5993.
[(triphos)(CO)2Re{C=C=C(C6H5)(p-C6H4NO2)}]* (3)
C
C
C
C
C
C
C
C
C
Re
P
C
C
C
C
C
C
C
O
C
O
P
1.4774410428 -0.6250351061 1.2419324974
1.3751381326 -1.9788906452 1.6063101991
0.5120166438 -2.3632211970 2.6432647459
-0.2600628532 -1.4050616434
-0.1701000359 -0.0352508346
3.3043085127
2.9440264973
1.9083827311
0.7227996949
-0.9440894000
-0.4737204279
-0.0287700338
0.3394131501
0.9929398127 3.6556358141
2.2792811540 3.7398463752
3.4648233012 3.8383359263
0.7298975025 5.2894168147 4.0753444366
-1.4832181066
-3.0686870360
-4.0853761780
-5.3031436821
-5.5143610211
-4.5034826219
-3.2799440481
6.3498322698
4.1082275018
5.4354697471 4.0846218508
5.7558609214 5.0070996646
5.0628966775 4.9788630190
4.0517525810 4.0309956504
3.7262642797 3.1144006433
4.4074318871 3.1433410788
2.5305850126 4.5514340529
3.6166738677 4.1219969659 3.9704125804
0.6005123355 5.1286067808 6.0152929734
5.0732424016 7.1789055980
4.0195836647
0.5174552694
0.9635205154
0.4306422079 4.6623889956
5.8026525597
1.6761004678
0.3390798065
C
C
C
C
-0.9252521714
-1.3092177258
-0.3472713820
4.5394539478 -0.0238764464
3.6313458066 -1.0196200761
2.8326272695 -1.6563008811
9

C
C
P
1.0035385309
1.3946482159
1.5675661821
0.5452914479
-0.3959154012
0.3142957431
-1.6931213956
-2.2441405241
-2.6715810226
-3.9118123854
-4.7391595134
2.9509669591 -1.2982601199
3.8614119502 -0.3055228679
7.5781129471 4.2662208699
8.8826644648 3.3776926272
8.3435912274 2.2684984701
7.5004711131 1.1789538240
7.6840802381 2.8067358115
0.6564095143 4.2799007658
1.3362445231 5.4459858270
1.0607740534 6.0195597623
0.1116167463 5.4076096336
C
C
C
C
C
C
C
C
C
C
N
O
O
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-4.3585414778 -0.5738661601
-3.1073182646 -0.3037072858
-6.0761116720 -0.1599725863 5.9925323840
-6.7670086865 -1.0296018538 5.4437020214
4.2502995938
3.6931930210
-6.4055078336
2.3352477360
2.8765334694
1.7267085143
-1.6888247534
-2.2444534643
-2.3631155164
1.2405909755
-0.0512391029
-0.3830500137
1.1651996429
-0.7410760542
-2.0066724032
0.5104229969
5.9264043384
7.8577107779
8.1691177833
7.1158885950
7.2182308597
8.4536815505
9.6264520714
9.4091495698
7.3345577320
8.0673813644
9.2481046018
2.0753470048
6.9814393875
1.3119231425
3.7708024395
5.5525711648
5.2934217283
1.9708599022
3.2261921314
2.9550876125
4.1420477382
0.3401839500
0.7638241610
1.7322655427
5.9005979877
-2.8064078548 -0.8137934333 2.7748383553
-5.0466796593 -1.2970806624 3.8071125828
-4.2571125442
-1.6908371868
2.4537742117
1.7615571856
-2.3633819370
-0.6491716040
-3.9276952960
-2.4827152537
-4.6617513405
-6.0861136859
-6.4656438561
1.9725254917 -2.7331023882 1.0851430092
0.7907713242 1.3945225420 1.6257405745
-0.9048866196 -1.7071858424 4.1340082835
0.4469617836 -3.4132454032 2.9425943833
2.1485498604 -0.3263653241 0.4311358142
1.5634051737
5.1552282721
6.9253464050
0.4611150507
3.9512971844 -0.0408660317
2.3424775051 -1.8008977213
3.5506326327 -1.3009809406
2.1265399546 -2.4350200807
6.5432552757
4.1234070230
2.9262262349
5.3130875314
3.5115921049
5.7520077580
2.4504679310
2.3848243502
5.7007139931
4.0125084913
α-phosphonioallenyl complex [(triphos) (CO)2Re{C(PMe3)=C=CPh(p-C6H4NO2)}]+ (7)
Re
C
1.75450
2.07750
-1.06880
-2.92620
2.03060
1.69480
10

O
C
O
C
C
P
H
P
H
H
P
2.38090
1.77990
1.80760
-1.42280
-2.46610
1.92320
2.83130
4.12940
4.94970
4.74480
1.81050
2.09150
3.30780
2.98720
4.09800
4.85450
5.09570
5.80800
2.80810
2.04570
3.25510
3.88820
4.50900
-2.70290
-3.12630
-1.62620
-3.99700
-4.20410
-1.83590
-0.62080
-4.84530
-5.21380
-0.98960
-3.37680
-5.03490
-4.25100
-3.36790
-4.18520
-5.07930
-4.26320
-2.68700
-4.18090
-5.75070
0.59840
-1.44380
-0.11320
0.28240
-0.73360
-1.12800
0.11940
0.84570
-4.04640
-1.29040
-1.39690
-0.42760
0.35710
-0.61120
-1.53940
-0.79640
-1.95770
-0.24030
1.39940
1.80980
2.18460
3.19540
2.31970
0.29060
-0.34740
0.70880
0.99050
1.78500
0.87930
1.42930
2.17210
0.66110
1.13830
0.99200
0.56320
0.80250
1.22790
1.07450
0.29440
0.72460
1.49190
0.87280
1.88670
1.95820
0.31160
0.81080
2.46440
2.42560
-0.51660
0.38980
3.30760
-0.73770
-1.07950
0.37440
-2.02350
-2.19200
0.20140
1.38650
-2.89660
1.46640
3.94860
5.11780
2.43210
2.74620
-0.38960
-0.98210
1.99540
1.88690
3.15800
2.32260
3.65920
1.46410
1.16270
2.22370
0.65480
-0.21280
1.01790
-0.78540
-0.86360
-1.78760
0.24140
-0.29330
4.19280
6.94630
5.04180
4.75130
6.11540
6.40500
4.61690
4.11410
6.53010
7.04670
1.69170
-0.33520
1.94160
0.39010
-0.62190
0.93740
2.92920
0.16770
-1.62970
1.11520
-1.67000
-3.58490
-2.15950
-2.15830
-3.10780
-3.11310
-1.81610
-1.80980
H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
11

H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
P
C
H
H
H
C
H
H
H
C
H
H
H
N
O
O
H
-0.95920
-1.66670
-2.23160
0.50000
-1.29780
-0.41340
0.49070
-0.40790
-1.30440
-0.44930
1.18590
-0.41350
-2.01900
-1.99570
-0.45610
-1.18740
-0.99180
-1.32180
-1.61100
0.05860
-0.47020
0.58960
-1.02260
-0.56190
-2.98750
-3.51400
-3.18070
-3.36400
-5.88130
-6.62710
-5.77930
-3.29160
-3.19250
1.07470
-1.21010
2.62170
4.61700
2.36500
3.87890
4.86990
3.36340
1.37220
4.08760
5.84140
3.15080
5.39480
-1.29420
-2.95240
-3.95800
-3.37130
-4.86500
-4.25070
-3.89900
-4.11760
-4.84510
-3.30750
-2.90630
-2.38810
-2.36860
-3.93810
2.43770
3.38510
1.92040
1.33040
-3.48940
-3.49370
-4.33250
1.91250
1.08320
0.87540
2.55190
2.13790
0.45660
0.41600
3.37270
2.64110
-0.34440
0.75900
2.18510
2.32610
0.81020
-0.06100
0.89810
0.67650
3.71590
3.52970
3.83060
4.63960
2.65870
1.84370
3.59890
2.74050
-1.41060
-1.12120
-2.53520
8.01060
γ-phosphonioalkynyl complex [(triphos) (CO)2Re{C≡CCPh(p-C6H4NO2)(PMe3)}]+
Re 1.654312 -0.413341 1.023710
C
O
C
O
1.080125 -2.073416 0.218726
0.702398 -3.073839 -0.268240
2.212467 -1.322716 2.634376
2.530528 -1.862695 3.629115
C -0.243329 -0.194556 1.826889
C -1.397318 -0.161110 2.296283
P
H
P
H
H
P
H
C
H
1.078759 0.815110 -1.021206
1.455764 0.092824 -2.195186
3.841623 -0.496482 0.026186
4.227500 -1.571647 -0.829940
4.980116 -0.548275 0.887936
2.437488 1.718666 1.947959
3.285222 1.607264 3.089680
3.624209 2.640603 0.799339
3.429731 3.717293 0.938914
12

H
C
H
H
C
H
H
C
H
4.649144 2.454775 1.166567
4.294958 0.971304 -1.061829
4.087927 0.690290 -2.108862
5.383455 1.131757 -0.990275
2.096395 2.360145 -1.277391
1.563419 3.195653 -0.789469
2.126355 2.580866 -2.357716
3.543084 2.281918 -0.706614
4.099392 3.085359 -1.224509
C -3.714815 -1.175713 2.227240
C -3.337976 1.216711 2.985236
C -4.416943 3.798741 2.868633
C -3.635146 1.925282 4.162529
C -3.610534 1.829723 1.741375
C -4.150353 3.113511 1.675574
C -4.173237 3.219014 4.113428
H -3.449769 1.491673 5.148543
H -3.384454 1.289997 0.816809
H -4.360837 3.598357 0.719430
H -4.401693 3.784586 5.019477
C -0.651581 1.247168 -1.482337
C -3.333584 1.732463 -2.210873
C -1.054261 2.529792 -1.900875
C -1.606366 0.209797 -1.425937
C -2.935447 0.449699 -1.798816
C -2.391009 2.769430 -2.257887
H -0.333874 3.350309 -1.964661
H -1.308060 -0.787354 -1.087345
H -3.662367 -0.367553 -1.758513
H -2.690230 3.769641 -2.585664
H -4.371299 1.919297 -2.503374
C 1.321592 3.044892 2.557282
C -0.287978 5.205755 3.364245
C
C
1.752084 3.908283 3.586193
0.067697 3.257824 1.952425
C -0.724916 4.344543 2.348112
C
H
0.946886 4.980828 3.990369
2.720148 3.745129 4.072828
H -0.300064 2.560959 1.192775
H -1.691932 4.511694 1.865426
H
1.286846 5.643726 4.791800
H -0.912348 6.049886 3.673035
C -2.723232 -0.198634 2.909322
P -2.328240 -1.000984 4.599457
C -1.060013 -0.041351 5.495014
H -0.287719 0.234517 4.760175
H -0.617132 -0.668061 6.284347
H -1.483446 0.869094 5.941718
C -1.609392 -2.636542 4.248814
H -0.718892 -2.503512 3.617793
H -2.344300 -3.263240 3.722493
13

H -1.328622 -3.112851 5.201348
C -3.762329 -1.309119 5.700991
H -3.425137 -1.875246 6.584017
H -4.506967 -1.905097 5.151258
H -4.228988 -0.370028 6.030064
N -4.939228 5.181794 2.807189
O -5.196265 5.741063 3.883159
O -5.068345 5.685736 1.681143
C -5.522357 -2.962962 1.009263
H -6.224320 -3.653998 0.532947
C -3.254221 -2.139005 1.312552
H -2.186885 -2.173611 1.072768
C -5.091778 -1.112905 2.523790
H -5.471995 -0.344904 3.205577
C -5.988887 -2.001972 1.918010
H -7.056727 -1.935642 2.147932
C -4.154886 -3.027717 0.707824
H -3.783976 -3.770578 -0.005223
β-phosphonium cyclopropenyl [(triphos) (CO)2Re{CC(PMe3)CPh(p-C6H4NO2)}]+
C
C
0.874712 0.510483 1.686189
0.753003 -0.571997 2.573096
0.767378 -1.882729 2.077459
0.900730 -2.117608 0.699402
0.993899 -1.036931 -0.193707
0.989836 0.281735 0.309550
1.050722 -1.327112 -2.009796
C
C
C
C
P
C -0.531553 -0.478027 -2.590876
C -1.714929 -1.411950 -2.965075
C -1.967551 -2.555171 -1.940083
P -0.882575 -4.066458 -2.154409
C -1.356677 -5.185459 -0.761341
C -1.471238 -4.746448 0.572443
C -1.803052 -5.655057 1.590259
C -2.016255 -7.009934 1.292861
C -1.909818 -7.452725 -0.035014
C -1.584974 -6.547512 -1.055645
Re 1.342214 -3.545542 -3.049813
C
C
P
C
C
O
C
O
P
2.560575 -4.328094 -1.541841
3.003294 -5.179115 -0.593325
2.913689 -6.773351 0.113037
4.610771 -7.412180 0.309991
1.374398 -5.281735 -3.890550
1.362014 -6.352393 -4.377065
2.932514 -2.902196 -3.948262
3.851101 -2.445080 -4.515137
0.038557 -2.631409 -4.863404
C -1.636252 -1.905265 -4.432088
C
C
1.978902 -7.940202 -0.935629
2.120191 -6.799536 1.763253
14

C
C
C
C
C
C
C
H
C
C
C
C
C
C
N
O
O
4.065803 -4.214593 -1.063441
5.164702 -4.745936 -1.953550
4.887441 -5.683349 -2.974546
5.914812 -6.233495 -3.752434
7.249527 -5.868235 -3.524669
7.541764 -4.945157 -2.511795
6.514318 -4.390915 -1.737106
8.052771 -6.299148 -4.129916
4.384594 -2.995474 -0.244756
4.818025 -1.817124 -0.900670
4.993390 -0.624855 -0.196165
4.740355 -0.612850 1.181815
4.364259 -1.769812 1.870863
4.190043 -2.952924 1.148174
4.819654 0.664075 1.915475
5.185804 1.666199 1.281321
4.492035 0.655300 3.113656
H -1.630748 -4.755140 -3.156787
H -0.307361 -3.472898 -5.961474
H
H
0.612468 -1.570330 -5.627641
1.989852 -0.328001 -2.398111
H -0.836929 0.211431 -1.786441
H -0.269876 0.150126 -3.461289
H -2.403446 -2.675798 -4.620214
H -1.845843 -1.074161 -5.125485
H -1.809582 -2.173154 -0.916455
H -3.015998 -2.892666 -1.998242
H -2.618567 -0.776807 -2.915126
H
H
H
H
H
H
H
H
5.004015 -1.840920 -1.979025
3.864446 -3.860323 1.669032
4.195127 -1.712612 2.948081
5.304162 0.299482 -0.688770
3.852583 -5.977824 -3.172133
6.767831 -3.678025 -0.946891
8.579048 -4.654262 -2.317659
5.669429 -6.948529 -4.544494
H -1.314700 -3.694244 0.828472
H -1.526263 -6.901769 -2.091452
H -2.098717 -8.502010 -0.282556
H -1.908899 -5.296172 2.618905
H -2.284397 -7.712498 2.087274
H
H
H
H
H
H
H
H
H
H
1.089780 1.134997 -0.370999
0.967551 -3.139175 0.312256
0.694624 -2.730200 2.766977
0.890228 1.535252 2.068447
0.663530 -0.388812 3.647560
0.936771 -7.594915 -1.020212
1.993925 -8.946557 -0.487373
2.431844 -7.971831 -1.937728
1.077583 -6.455785 1.672212
2.666114 -6.126698 2.442136
15

H
H
H
H
2.133665 -7.820950 2.176528
4.587210 -8.412725 0.768795
5.188337 -6.726789 0.948584
5.094181 -7.459616 -0.677821
[(triphos)(CO)2Re(=C=C=C(p-C6H4NO2)2)]+ allenylidene
Re
C
O
C
O
C
C
C
P
2.3216533966 -0.6332640356 0.6884345321
2.3473578341 -2.4859940999 0.0701967272
2.3737496967 -3.5852946928 -0.3216912428
2.5510903089 -1.1198855821 2.5605091309
2.7013241367 -1.3969068415 3.6856444641
0.3556861543 -0.6899487381 0.9238730285
-0.8933459944 -0.7350679675 1.1586610207
-2.2140729701 -0.7300836963 1.5199164047
2.2965578018
2.8540891366 -1.0007150256 -2.4886268757
4.7345648842 -0.3974054292 0.3633468410
0.0300398913 -1.6786749034
H
P
H
H
P
5.3664626192 -1.2682723759 -0.5734853021
5.6303437160 -0.6120913728 1.4499055260
2.4290595293
3.3107970986
3.2176873123 2.8356795075 0.0891316212
1.7181110799
1.3682685588
H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
1.9176366150 2.4701730016
2.3905053617 3.3197720906 -0.4593374946
3.7430007981 3.6404031505 0.6305080922
5.2865726290 1.2909718986 -0.2520842033
6.1187265545 1.1334913720 -0.9576358282
5.7067325061 1.8322453455 0.6125585365
3.4503550854 1.4583864248 -2.0948306794
2.8472349930
4.1897050963
2.2060537587 -2.6373434610
1.0776563466 -2.8201811118
4.1817852096 2.1532006932 -0.9184737448
4.7314883933 2.9883561309 -1.3924531486
-2.5814915570 -0.1713503604 2.8400272534
-3.1754114774 1.0253815329 5.2889847964
-1.6673882398 -0.2516481399 3.9205898266
-3.8046755171
-4.1024080467
-1.9644601796
0.5216431738
1.1274999899
0.3362802780
3.0264140544
4.2482939014
5.1484307658
-0.7280155652 -0.7931982731 3.7830218032
-4.5056618008
-5.0281222819
-1.2840785638
0.6224912433 2.1941998423
1.6843220995 4.4097117421
0.2774204119 6.0006855477
-3.2457393658 -1.2312875724 0.5922173609
-5.1747293581 -2.1531461321 -1.2005515013
-3.0038163119 -1.2021713898 -0.8043412105
-4.4722059802 -1.7658174129 1.0639207864
-5.4384515903 -2.2304648948 0.1700293517
-3.9673713099 -1.6531180021 -1.7029841251
-2.0558975083 -0.7984047789 -1.1722525466
-4.6553361797 -1.8442597159 2.1382932190
16

H
H
C
C
C
C
C
C
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
N
O
O
N
O
O
-6.3882199177 -2.6501103345 0.5088831720
-3.8127056401 -1.6202582236 -2.7833599377
0.7638478815
-1.6203701971
0.0950309800
0.3240347529 -2.6442536674
0.6860917271 -4.1026007213
1.5641549845 -2.6181386403
0.2257854023 -0.7358034780 -3.4025822610
-0.9598475311 -0.5519029431 -4.1289419334
-1.0893792163
0.4989227400
1.7428533534 -3.3467268607
2.4046713687 -2.0423744153
0.7347882634 -1.7050246600 -3.4376812434
-1.3582665081 -1.3765640211 -4.7279113313
-1.5936065771
-2.5388086993
0.9711641283
-1.2813218396
1.0158400775
-0.2131137795
-1.3290903794
-0.1098187245
1.9265611155
-0.2735634789
-2.2440825056
-0.0671400328
-2.1573236226
2.7135712245 -3.3302581658
0.8310457471 -4.6786683843
2.6246252372 2.0003667734
3.9743181873 3.0079617837
3.2282843418 3.2730326787
2.6912306663 1.2386155143
3.3736222578 1.7401787012
3.8968758759 3.7739869047
3.1740532856
2.1963097652
3.4276852897
4.3587243711
4.4996704181
3.8788652286
0.2635357837
1.1425325536
4.7647209027
3.3992446897
-6.2112819422 -2.6143174730 -2.1586734198
-5.9307854478 -2.5496135139 -3.3636472861
-7.2774918221 -3.0233954727 -1.6825744763
-3.4745980967
-2.6145413130
-4.5562050416
1.6932806644
1.6140708290
2.2894587474
6.5804649543
7.4679947268
6.6700380089
α-phosphonioallenyl complex [(triphos)(CO)2Re{C(PMe3)=C=C(p-C6H4NO2)2}]+
Re
C
O
C
O
C
C
P
H
P
H
H
P
1.5832837026 -1.0201846600 2.0520150799
2.1449968366 -2.8619200486 2.0087367072
2.5467344392 -3.9684501481 1.9961390646
1.5367960897 -1.0163230093 3.9806044367
1.5817388749 -0.9588988666 5.1513499069
-1.3570653524 -1.2589578977 3.1442999779
-2.0856949453 -0.8850177783 4.2071943596
2.1323866534 -0.7062250680 -0.3316989194
3.3567616111 -1.3956643794 -0.5881848219
3.8671769456 -0.3525684772 2.2359727721
4.8772098013 -1.3545787346 2.1251880537
4.2720926719
1.0469774126
0.8854015623
0.1789918736 3.4967584237
1.3873488163 2.0682835978
1.9709648023 3.3585921715
H
C
H
H
C
2.4731424616 2.4522723591 1.4457262119
2.0268270045 3.3693516318 1.0259486960
3.0603587729 2.7630231545 2.3282601124
4.5320611552 0.9475002839 1.0558253619
17

H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
P
5.1267956637
5.2282527719
2.6694694623
1.7669937757
3.3053409764
3.4157333611
3.9341926447
-2.2649642803 -1.7730317516
-2.7441694437 -3.5165601637
-1.3853539282 -2.8493604991
-3.3885560088 -1.5972288540
-3.6319059767 -2.4628521220
-1.6189811394 -3.7201449849
0.4371321442
1.5964879626
0.2793207739
1.6123699280
1.0450184503 -0.7350814378
1.6139638762 -1.0181706559
0.9856857497 -1.6343657562
1.7953384874 0.4019118364
2.6358899366 -0.0956672078
5.3911626237
7.5330469552
5.6596551323
6.2345668955
7.3027870419
6.7246125449
-0.5021428927 -2.9944544607 5.0311427530
-4.0920910483 -0.7835795186 6.0400294408
-4.4994521180 -2.3449570841 7.9559313971
-0.9479474786 -4.5519278567 6.9507245057
-2.7268144074
-3.7097139523
-2.5611521525
-3.4367518403
-3.9291119924
-3.0488002776
-2.0210895305
-3.5952926671
-4.4647696857
-2.9094615256
1.2960147369 -1.2461028557 -1.8904166477
0.0591324401 -2.1866282082 -4.2443377961
0.4106021176 -0.4177052474 -2.6101446480
1.5567571960 -2.5495466821 -2.3656131110
0.9389207969 -3.0165997112 -3.5336120553
-0.1999653338 -0.8880969779 -3.7831984192
0.4666356538 4.1880558670
3.0855435371 4.1169647955
1.3305302348 5.2971554214
0.9389835176 3.0640382504
2.2448410110 3.0206524783
2.6383835790 5.2670693464
0.9760313291
0.2737971751
2.6319817803
3.3248885594
6.1795818651
2.2098033560
2.1522256785
6.1053424859
0.1977035743
0.6010884115 -2.2714101324
2.2652128830 -3.1961018056 -1.8342917911
1.1590812170 -4.0247922459 -3.8974222684
-0.8723847667 -0.2309003751 -4.3430981733
-0.4139933956 -2.5472445254 -5.1622442847
-0.4066823689
-2.5474397611
-1.0797934012
-0.8232135487
-1.8900418812
-2.1400817322
-0.7713883056
-0.3244203248
-2.2251920497
-2.6519044311
-3.3793491691
2.1292050964 1.2169716066
3.3094152128 -0.1869181685
1.4128600764 0.2122850418
3.4414044400 1.5226316750
4.0255576696 0.8265914149
2.0024732286 -0.4936702811
0.3848182662
4.0090826627
5.0327261733
0.0013186626
2.3157743493
1.0903828070
1.4388279200 -1.2810845895
3.7697905918 -0.7277471952
-0.5832737505 -1.6106330900
-1.4952718848 -2.7672526109
2.1283654089
1.0715965017
18

C
H
H
H
C
H
H
H
C
H
H
H
N
N
O
O
O
O
-2.1706691834 -2.0251071490 -0.4576153461
-2.8119592564 -1.1707725293 -0.1932057336
-2.7695768484 -2.7781109023 -0.9942636945
-1.3543081045 -1.6830132987 -1.1116912694
-0.4603552809 -4.1714531211
0.5449314970
0.3413564718 -3.8160317588 -0.1182398591
-1.0888220768 -4.8939224213 0.0003841717
-0.0121491634 -4.6617357631 1.4209794669
-2.9253554875 -3.4950534437
1.9514809637
-3.6165162496 -2.6990016641 2.2648467453
-2.5767312133 -4.0247104871 2.8512540449
-3.4515662637 -4.2004012384 1.2893226143
-3.0078407585 -4.4447486197 8.6534962144
-4.1346250365
-4.0276248347
-4.5457978119
4.4956552548
5.1846892873
4.9030443102
4.0365100555
5.0604864362
2.9362153893
-4.0082450349 -4.2233553089 9.3517583164
-2.2118017906 -5.3824655449 8.8113899089
γ-phosphonioalkynyl complex [(triphos)(CO)2Re{C≡CC(p-C6H4NO2)2(PMe3)}]+
Re
C
O
C
O
C
C
P
1.6217054684 -0.2472318584
1.1850532379 -2.1032278871 0.9543069929
0.9271369390 -3.2357239488 0.7802423628
2.0385542999 -0.6222693921 3.1115363588
2.2979930551 -0.8472168054 4.2366031794
1.2659037548
-0.3697308124
-1.5627629270
1.3029093072
0.0381019677 1.7938466625
0.0361300440 2.1555657450
0.2142998267 -1.1196437962
H
P
1.6828061818 -0.9215951671 -1.8949638557
3.9126388688 -0.5648705850 0.6012463467
H
H
P
4.3144887251 -1.8175261750
4.9149527129 -0.4965232882
0.0475423778
1.6159536145
1.6231976959
2.3976683262
3.3820296668
3.4183785329 2.7654760732
2.0451994529
H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
2.0867656256 2.6556099027
0.2045909415
2.8650494541 3.6507841917 -0.1525299036
4.3626391880 3.1406323372 0.6349404824
4.6191684467 0.6262739797 -0.6778515962
4.8099003403 0.0541307546 -1.6015954214
5.6016809472 0.9710273409 -0.3150332278
2.4622195441 1.5047886522 -1.8339364867
1.8632312491
2.7529544098
2.4209697495 -1.9770468315
1.1619323476 -2.8413885073
3.7238610436 1.8475181028 -1.0038208141
4.3391711121 2.4745904047 -1.6779536603
-3.8111774573 -0.9343683268 1.6480985187
-5.3608799635 -2.3303448779 -0.2140486647
-3.4125003965 -1.0134988683
-5.0083124456 -1.5751131380
0.3010149185
2.0390374136
19

C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
P
-5.7856937785 -2.2811551565
1.1156241329
-4.1882831942 -1.7014968250 -0.6366745491
-2.4821483298 -0.5281976977 -0.0045845271
-5.3642042705 -1.5170485209 3.0707285049
-6.7122508349 -2.7840345714 1.4012044947
-3.8952072303 -1.7595431161 -1.6869555694
-3.5956056524
-4.7030062548
-2.7728277554
-4.9860811578
-5.5442017749
-3.3199902540
-1.6878949024
-5.6463664500
-6.6163482447
-2.6940060835
-0.2889141641
-2.7349282047
-0.9619097916
1.1942184525 3.1035375857
3.6044259261 3.9913110587
2.2172684442 3.6201992679
1.4173634880 3.0263163773
2.6234088630 3.4637908432
3.4205331273 4.0757891048
2.0795979704
0.6670317097
2.8203567563
4.2233606566
3.6159421534
2.5874481976
3.3942094694
4.4712941509
0.5618018672 -1.9664538833
1.0681389831 -3.2633247726
1.7832860415 -1.7628741457
-0.8552131779 -0.4065195542 -2.8193755073
-2.0743602210 -0.1523821982 -3.4644183970
-2.1767495562
-0.5368208645
2.0348039744 -2.4131465356
2.5463513612 -1.1017367828
-0.3411347532 -1.3588806275 -2.9881624248
-2.5004254875 -0.9053714321 -4.1347420890
-2.6878201914
-3.6818640767
1.3843126818
-0.1186824761
1.9389415394
0.0633159511
-0.6786925404
1.1864435564
2.9592031484
-0.3902653764
-1.7033802877
1.6208988419
-0.7032791992
2.9896827079 -2.2579162967
1.2681776544 -3.7732049643
3.4733473349 2.1684820394
5.7407918876 2.8742337391
4.4583470814 3.0105778316
3.6171935088 1.7019971679
4.7568149780 2.0457751785
5.5852031058 3.3647543033
4.3448185735
2.8194610058
4.8687073675
6.3430423406
6.6244358648
3.3932273873
1.1046079142
1.6787328734
4.0234638198
3.1474259689
2.6353318466
4.2038480721
5.2608403472
-2.9346070096 -0.1293319713
-2.6434686002 -1.2130475567
-1.3844169893 -0.4286979751
-0.4722275323 -0.2445203732 4.6772657920
-1.1612514608 -1.1103848670 6.0970592046
-1.7725951529 0.5198318681
-2.0246156931 -2.8404789206
-1.1606956878 -2.6858176743 3.0075434335
-2.8142350855 -3.3788827272 3.1271264725
-1.7179462921 -3.4249047512 4.5532556268
C
H
H
H
C
H
H
H
C
H
H
5.6612926917
3.6718455336
-4.0964723881 -1.4560571122
-3.7400495753 -1.7453847698 6.3047951968
-4.7596045220 -2.2454463120 4.9226424234
5.3031965423
20

H
N
N
O
O
O
O
-4.6560283194 -0.5109337002 5.3861854084
-5.2914788391 4.8881315576 4.4438993080
-6.1820027188 -3.0693310847 -1.2026833770
-4.5100906230
-6.5177731459
5.7364874909
5.0191187420
4.8968215069
4.3334707669
-7.1973865065 -3.6385297498 -0.7805045994
-5.7921521143 -3.0610983693 -2.3780232656
β-phosphonium cyclopropenyl [(triphos)(CO)2Re{CC(PMe3)C(p-C6H4NO2)2}]+
Re
C
O
C
O
P
H
P
H
H
P
0.7326656475 0.6412239671
0.7346168886 -0.8336554536
1.5584266959
2.7992150329
0.7377969811 -1.7543400919 3.5312638823
0.3759849722
0.2213221962
1.9873029311 2.9043626016
2.8505646620 3.6816174611
1.5503874496 -0.8561761113 -0.2077504850
2.4811229847 -1.7782111730 0.3594094360
3.0957417187
3.7640539553
3.5099947398
0.9892751283
0.9324990478
0.9794894795
1.9362515693
0.1422444689 2.8766286791
2.2311796437 2.4841936014
2.4536024632 -0.1036857257
3.7699324698 0.4409605293
H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
2.7406457663 2.5178655922 -0.8101855713
2.6574423190
3.3160514063
4.2311351587 0.8346783608 0.4516841687
4.6322382144 -0.1929599059 0.4244765770
2.9523486311 -1.8200786072
3.2406260847 -0.2044196414
5.0916810638
2.6697854330 -0.0047272050 -1.4459636799
2.0337075919 0.3591525081 -2.2717365540
1.5069038722 0.6030474900
3.3329132066 -0.7770119802 -1.8703912193
3.5120065486 1.1725758945 -0.8791446999
4.3179473490
-3.2006549406
-3.9009263221
-2.7398723230
-4.0670939001
-4.4248348893
-3.0806218632
-2.0899479567
-4.4465250948
-5.0789232040
-2.7096592413
-3.0335977405
-3.7682923491
-2.4415274795
-4.0039788204
-4.3734965738
-2.7999866325
1.3332584772 -1.6188256373
2.0635078702 0.8177889863
3.9970381296 -1.0757336926
3.3943737655 0.9426232033
1.7490121205 -0.2452300283
2.7068709655 -1.1968871087
4.3645331149 -0.0026402813
3.6600993745 1.7826130809
0.7257789828 -0.3414488054
2.4783998428 -2.0411347606
5.3902894430 0.0574605562
1.2051060990
1.4518077908
0.3914711883
2.1492167231
2.2772385500
0.5091989817
3.2316153217
5.9364728967
4.2290042715
3.6431187426
4.9850341793
5.5737553498
-1.6797911139 -0.3406514525 3.9487625143
2.7882523944 2.9004387170
2.9979729615 5.3089399749
-4.4888342842
-5.1280026947
21

H
C
C
C
C
C
C
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
P
-2.3460130365 -0.1099555189 6.3511385923
0.6327073140 -2.0991998614 -1.2174942020
-0.7695814478 -4.0659725707 -2.6811589371
-0.0791092856 -1.7484140837 -2.3813395041
0.6385138287 -3.4467315835 -0.7970990568
-0.0615057745 -4.4221114808 -1.5225126227
-0.7698292156 -2.7290115795 -3.1099625508
-0.0906973568 -0.7133990250 -2.7360294142
1.2106563583 -3.7423699790 0.0900073145
-0.0351605204 -5.4651040583 -1.1917248189
-1.3004707770 -2.4464029822 -4.0246066511
-1.3014770020 -4.8289868587 -3.2570679833
-0.0460765620
-1.5427187044
0.1239110515
-0.9840210640
-1.7205280573
-0.6252294491
0.8301747642
-1.1580448696
-2.4532507512
-0.4992440541
-2.1312929904
-2.6998189159
2.6761691169 -1.6083604729
2.9853015788 -3.9729218263
3.8222075694 -2.4144315740
1.6994625631 -1.9830169620
1.8511484419 -3.1687242442
3.9762959580 -3.5871495744
4.6073861601 -2.1210416050
0.8427868062 -1.3241821616
1.0893952842 -3.4526004171
4.8765100900 -4.1958058759
3.1114021381 -4.8858230658
1.0132372159 1.7723037246
-3.2295009230 -1.9573485883
-2.1250533329 -3.2664906645
1.2586255604
1.8901686836
C
H
H
H
C
H
H
H
C
H
H
H
N
N
O
O
O
O
C
C
-1.2684980718 -3.3737328625 1.2066241589
-2.6705100246 -4.2224112666 1.9413465386
-1.7569009529 -2.9933817163 2.8900010175
-3.7665282938 -2.4893195736 -0.4077837759
-2.8868698169 -2.5638932553 -1.0667157965
-4.4669291820 -1.7489391200 -0.8229782353
-4.2660145366 -3.4697615156 -0.3505455404
-4.7116923079 -1.8867148836
2.3197155977
-5.2280215309 -2.8590885001 2.3128448111
-5.3931600066 -1.1067982272 1.9471388890
-4.4122145124 -1.6288452483 3.3469023602
-4.1674145841
-4.1694151064
-3.6340776345
-5.0096066628
-4.8137227968
-3.7103767296
-1.3244031039
1.5660290247
4.9780011192 -2.1454343359
7.3553634311
0.7850505025
2.4295333980
8.1586386872
7.6422636989
4.5839843517 -3.1309844780
6.1203976522 -2.0000896567
0.3266500666 1.3732744349
-2.4610712589 -0.3885057889
1.2653371053
[(triphos)(CO)2Re{C=C=CH(p-C6H4NO2)}]*
Re
C
O
2.0146824891 -0.1211762620 2.3698721901
1.8720757695 -1.8709174011
1.7799128876 -2.9219742388
3.2038785210
3.7064808791
22

C
O
C
C
P
H
P
H
H
P
2.2608174664
2.4118196928
-1.2104961620
-2.5561141916
1.9680247533 -1.1379993273 0.1349350613
2.6767493998 -2.3736077533 0.0952703246
4.4372164442 -0.2659413731 2.0397032620
5.1654267471 -1.4292862086 2.4237295702
5.2154938493
2.2464535886
2.7007832501
3.5924656667
3.2508299102
4.4547252977
5.0429459327 -0.0264073985 0.2785359238
5.2548264506 -1.0266017904 -0.1367023664
6.0072247279
2.8920449710 -0.1589343917 -1.1664478170
2.1378535299 0.4623689003 -1.6790749230
3.2642421005 -0.8778206449 -1.9155278995
0.6794867792
1.1494946290
0.2009102403 2.5693770711
0.3521888176 2.6053666390
4.1415148793
5.1980296554
0.6885405649
2.0526988043 1.2323744698
3.0977890031 2.0877434906
2.0949606033 -0.0733405821
2.7520722177 -0.8903032368
2.7560202520
H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
C
C
C
C
C
H
H
2.6109094125
0.3838074626
0.5058213622
0.3205229588
4.0548790916
4.6467244580
0.7293923211 -0.6488489323
0.9834976596 -1.5477894407
-3.4928654461 -0.4219686505
-5.3645707507 -1.8817275372
-3.0690611182 -1.4548017783
-4.8799646852 -0.1417918236
-5.8218613795 -0.8700267463
-4.0033021708 -2.1845701438
3.3980023604
4.8538328628
4.2766606523
3.2786656866
4.0025259946
5.0061038176
-2.0006123394 -1.6690295940 4.3698923202
-5.2114979518 0.6547089041 2.6049504483
-6.8945225408 -0.6799540660 3.9267461153
-3.7140578687 -2.9850679293 5.6901224586
0.4065527791 -1.6604341676 -0.6507242566
-2.0070885562 -2.4698639720 -1.8329978089
-0.6269064223 -0.7229976776 -0.8550577745
0.2219812041 -3.0046239763 -1.0308265075
-0.9863238240 -3.4055615356 -1.6167968313
-1.8247836229 -1.1306861441 -1.4548240221
-0.5033042191
0.3178696163 -0.5385148456
1.0152589614 -3.7411419194 -0.8662254133
-1.1273297962 -4.4514156337 -1.9043053381
-2.6226874010 -0.4006545388 -1.6210263497
-2.9481027199 -2.7852076376 -2.2932620446
0.7628528845
-1.6011713920
0.5129941027
-0.1872864016
-1.3582665200
-0.6654080019
1.2346575864
-0.0097346612
2.8706453706 0.5185298877
4.0755852736 -0.4278692176
2.9586259482 -0.8640745293
3.3855364788 1.4257752756
3.9901933821 0.9518045133
3.5592761691 -1.3336115784
2.5761032120 -1.5928307174
3.3232855442
2.5045146144
23

H
H
H
C
N
O
O
H
-2.0784102084
-0.8433573395
-2.5142232425
0.0565162470
-6.3623262791 -2.6702596616 5.6246448638
-7.5547905554 -2.3821830835 5.4583623755
-5.9244262506 -3.5552285668 6.3712666541
4.4053641758
1.6635294371
3.6306253049 -2.4106138113
4.5525489884 -0.7959332037
0.0950405720 2.4752325226
-3.0060361193
1.1325761974
1.9690286603
α-phosphonioallenyl complex [(triphos)(CO)2Re{C(PMe3)=C=CH(p-C6H4NO2)}]+
Re
C
O
C
O
C
C
P
H
P
H
H
P
1.8866965690 -0.9223920572 2.1783503421
2.7146333532 -2.6239236114 2.4769282431
3.3103561150 -3.6276284439 2.6626487494
1.5446925211 -0.7068714436 4.0691831340
1.3174898028 -0.5889059692 5.2150254090
-1.3056803297 -1.0277474286 2.0592759817
-2.4591255279 -0.3646147434 2.1042823098
2.3384462395 -1.1123811066 -0.2141848394
3.4442170375 -1.9733009167 -0.4833380397
4.0538166802
5.1681947206 -0.7458672144 2.7144540860
0.0638022019
2.3462440102
4.2305428840
1.3197943288
1.5097025122
1.0803482850 3.3354417152
1.4680129980 1.7924603907
2.1864103334 3.0084931783
H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
2.5639235644 2.3690512576 0.6856577058
1.9654173971 2.9459990949 -0.0387973433
3.0816150223 3.1124464072 1.3159434764
4.7202737588 0.9356021807 0.8290072719
5.3309942094 0.2110642653 0.2631275130
5.4026584024 1.7366396603 1.1586814278
2.9585127358 0.4683317785 -1.0202847874
2.0927775283 0.9194788933 -1.5364751764
3.6717060639 0.1769000445 -1.8097573308
3.6051838551 1.5155328086 -0.0781976165
4.1153198374
-3.1742647515
-4.6242948896
2.2299073777 -0.7519633503
0.0216226525
0.7597150950
3.3294719109
5.6069755737
-2.6335643037 -0.1770815551 4.6244792119
-4.4579129261
-5.1875705227
-3.3533008923
0.6069705658
0.9751325476
0.1896182630
3.2146203946
4.3451832044
5.7612826944
-1.6326953621 -0.6063991876 4.7336793544
-4.8851679942
-6.1809545392
-2.9559239349
0.7707607328 2.2198899822
1.4237669866 4.2762231138
0.0507510564 6.7692026682
1.1722721144 -1.7894222536 -1.4579723390
-0.6201457575 -2.8132771247 -3.3703022802
-0.1619438575 -1.3322372403 -1.4964151864
1.5968436753 -2.7695241680 -2.3781283250
0.7014321034 -3.2801977597 -3.3284112444
24

C
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
P
-1.0492544081 -1.8388405167 -2.4558378345
-0.5080304074 -0.5908644719 -0.7693630378
2.6289488635 -3.1359180678 -2.3538952655
1.0399040937 -4.0404684750 -4.0385318141
-2.0809121611 -1.4747987864 -2.4875092370
-1.3161960138 -3.2093472563 -4.1154968028
-0.2799059791
-2.7242169408
-0.7097213448
-1.0860681264
-2.3037384428
-1.9254563995
-0.0937957335
-0.7661174085
-2.9205095910
-2.2440007322
-3.6690576913
2.2386107699 1.3081718827
3.4406798772 0.6004359834
2.2398904332 -0.0339866458
2.8419948398 2.2921662403
3.4381553546 1.9376951827
2.8415945031 -0.3854313711
1.7849112688 -0.8180409656
2.8496344175 3.3394312457
3.9070456543 2.7099699465
2.8513996894 -1.4323074123
3.9177479056
0.3237452827
2.0394760724
2.2000933839
1.9910170989
-0.1765934689 -1.7105967276
-0.5376803980 -3.4760335601
-2.3164787588 -3.8504925717
C
H
H
H
C
H
H
H
C
H
H
H
N
O
O
H
-2.9092929420 -3.2889278146 2.7277968291
-2.4816818328 -4.9300699604 2.1321878714
-2.6415702849 -3.5598453505 0.9809104932
0.3427720079 -4.5184655926 0.9863310324
0.1387926165 -4.1501068946 -0.0303573527
-0.0143733119 -5.5561729339 1.0814004072
1.4244434446 -4.4937565324 1.1765234421
-0.0896576608 -4.0736898382
3.8688427773
-0.6317107306 -3.4801751529 4.6208357008
0.9913306496 -3.9673871934 4.0339521498
-0.3702820063 -5.1341172798 3.9688169855
-5.3882345690
-6.5030756504
-4.8616130264
1.1500643082
1.6638646418
0.9375749835
6.8088840805
6.6316516021
7.9116602327
-2.9356377352 -0.0804637281 1.1551487313
γ-phosphonioalkynyl complex [(triphos)(CO)2Re{C≡CCH(p-C6H4NO2)(PMe3)}]+
Re
C
O
C
O
C
C
P
1.8854832540 -0.3029905028
1.7516230978 -2.2110055152 1.0644413733
1.6461270550 -3.3728191200 0.9171211689
2.3079060363 -0.5586256838 3.1932184302
1.3263395018
2.5183235714 -0.7226411508
-0.1081807932 -0.2785540745
-1.2781019323 -0.3101285642
4.3383102055
1.8765702524
2.2967540585
1.4527920732
0.0387861170 -1.0571169777
H
P
2.1024071060 -0.9705710323 -1.8291614408
4.1925750924 -0.1764865328 0.6637350495
H
H
P
4.9162357377 -1.3395347333
5.1361847689
2.1824399985
0.2623715585
0.2826077066 1.6337882970
2.1176655315 1.5942623286
25

H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
P
3.0355639361
3.1826436675
2.6058039029
4.1167688334
4.5845276467
4.7008878036
5.5666667509
2.2596611049
1.4947198421
2.5025132578
3.5205283662
4.0034399660
-3.7607506304 -0.6198960358
-5.8559004162 -0.9425976234
-3.5170851592 -1.1553465073
-5.0716175679 -0.2431248354
-6.1291835635 -0.4005775419
-4.5671871742 -1.3246150183 -0.3124174197
-2.4894039809 -1.3979823136 0.3072130429
-5.2656277447
-7.1518079213 -0.1037526959 1.5728333410
-4.4019874415 -1.7269856302 -1.3134181950
-0.1788756636 -0.0420027954 -1.8983401922
-2.6696665975 -0.2265239545 -3.1992777422
2.4352864050
2.9362696628 0.2094633389
3.8204959997 -0.1104973262
2.6924933695
3.3173724629
0.6570704836
0.9762335553 -0.7723619440
0.3546818728 -1.6768218210
1.4402152139 -0.5830094785
1.5652360506 -1.7788563459
2.3613464523 -1.7924535376
1.3451880189 -2.8320783857
2.0747929648 -1.0319941840
2.7784828026 -1.7367940376
1.8730429910
0.0692593653
0.5951173552
2.2309199170
1.3294876699
0.2034340945
3.2129146267
-1.0998521564
-0.5225591884 -1.2041325497 -2.6180780733
-1.7635435384 -1.2951135129 -3.2636589708
-2.3356948998
-0.8558127427
0.1848505838 -2.0377554074 -2.6856307277
-2.0146798203 -2.1973135132 -3.8298058643
1.0218204583 -1.8237385021
0.9295473517 -2.4771885754
1.9298765990 -1.2620973072
-3.0398322510
-3.6348831287 -0.2941463126 -3.7106137417
1.7654668474 -2.4257879164
0.8395204505
-1.1901611816
1.1273904405
-0.4752066398
-1.4835478252
0.1148684846
2.1423905356
-0.7120589586
-2.5043574802
0.3446903001
-1.9791573734
-2.6076324303 -0.4412139374
-2.4943116412 -1.9492676792
-1.2478070393 -1.6201212288
-0.3033688585 -1.3304447208 4.7877005684
-1.0929683015 -2.5221726960 5.8851661197
-1.5919772323 -0.7986806687 5.9209026282
3.3231117785 1.9369953222
5.2170629604 2.3820482836
4.5280061315 2.6110615815
3.0647151089 1.5046577947
4.0148179187 1.7234185913
5.4702029992 2.8312527061
4.7307534396
2.1038202561
3.8099801511
6.4016571028
5.9554825995
2.9701259151
1.0392706367
1.3850281075
3.3571985588
2.5538102691
2.8622101999
3.9890778055
5.2729512100
C
H
H
H
C
-1.9805282597 -3.3802280336
2.9942704445
26

H
H
H
C
H
H
H
N
O
O
H
-1.0369856220 -3.1313672218 2.4847399098
-2.7539582740 -3.6035449304 2.2433020469
-1.8375026860 -4.2554543573 3.6463129750
-4.0780529189 -2.3459321427
4.8125860051
-3.9645770560 -3.2489481652 5.4331159086
-4.8563988707 -2.5204625285 4.0544231857
-4.3857981282 -1.5074920249 5.4566101268
-6.9652309072 -1.0908824691 -0.9044042355
-8.1013871548 -0.7832805843 -0.5188390978
-6.6723201979 -1.5093898750 -2.0339614566
-2.8616522560
0.3900084403
3.5554155978
γ-phosphonium cyclopropenyl [(triphos)(CO)2Re{CC(PMe3)CH (p-C6H4NO2)}]+
Re
C
O
C
O
P
H
P
H
H
P
0.9013412474 0.3322031868
0.9799748139 -1.2480029296
1.6291228934
2.7297868483
1.0116070422 -2.2194038016 3.3934766096
0.5346898342
0.3884132065
1.4939117151 3.1435524697
2.2339204749 4.0388357375
1.6822267508 -0.9503363176 -0.2949449558
2.7053298579 -1.8639526206 0.1014303477
3.2584002447 0.7867908664
4.0842234493 -0.0938700044 2.6416149883
1.8813624316
3.6401266382
0.9418910073
0.9979193780
1.9949630526 2.5403803348
2.3414267142 0.2190523297
3.5568221363 0.9613320017
H
C
H
H
C
H
H
C
H
H
C
H
C
C
C
C
C
C
H
H
H
H
C
C
C
2.5438697368 2.5353846356 -0.7709129053
2.2580265542
3.1433783440
4.2585136154 0.9100908184 0.2928408519
4.7687870845 -0.0561696303 0.1392904286
2.9365506581 -1.7578160290
3.3192786699 -0.2755964187
5.0502663326
2.6313294311 0.0617436171 -1.5491837578
1.9081587751 0.4254972676 -2.3002270426
1.6625058019 0.4418083617
3.3187900061 -0.6219129503 -2.0749841588
3.4145363589 1.2671476396 -0.9584557414
4.1524866628
-3.0683303608
-4.1512373608
-2.7650347022
-3.9191512833
-4.4641020332
-3.3010885805
1.5394516631 -1.7362361505
1.2673474520
2.4234551482
0.7468442943
2.3927410975
2.9747384721
1.3180953894
2.6875845311
5.0003031986
3.9672081289
2.6066728541
3.7532249447
5.1233433920
-2.0882432726 -0.1099976286 4.0542900925
-4.1613240984
-5.1294977831
-3.0773119449
2.8113655322 1.6236572896
3.8397449202 3.7069490639
0.9325775932 6.1206731048
0.7152096696 -2.1476428486 -1.3075451667
-0.7724612105 -4.0482534417 -2.7664080970
-0.1171726286 -1.7385599517 -2.3674231250
27

C
C
C
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
C
P
0.7944990327 -3.5193824809 -0.9854603135
0.0527106092 -4.4632029382 -1.7097845900
-0.8526578793 -2.6863360702 -3.0946586182
-0.1864264349 -0.6821807068 -2.6454234771
1.4528906850 -3.8553732860 -0.1763255015
0.1362424045 -5.5256861656 -1.4609162783
-1.4797234064 -2.3595657500 -3.9299357772
-1.3379862054 -4.7861266055 -3.3431828278
-0.3638933599
-2.2916761254
-0.5177751648
-1.1928467932
-2.1492182405
-1.4796129682
0.1064436777
-1.1059096736
-2.7930169071
-1.5988093575
-3.0423622705
-2.5402953041
2.8071852922 -0.9867727858
3.5180736203 -2.9075713543
4.1541268789 -1.3744561896
1.8232630528 -1.5565247895
2.1784068765 -2.5190809007
4.5057461936 -2.3301160400
4.9334655382 -0.9235964077
0.7853680254 -1.2183823169
1.4095144169 -2.9575762298
5.5541433137 -2.6192053240
3.7961896224 -3.6531068381
0.6601711433 1.4310254663
-3.0146761604 -2.3612065749
-1.8457454247 -3.6925554249
1.4459570783
1.8763414704
C
H
H
H
C
H
H
H
C
H
H
H
N
O
O
C
C
H
-1.1247052288 -3.8171124016 1.0536693366
-2.3949910182 -4.6349318030 2.0284101133
-1.2995537212 -3.4261762691 2.7935647703
-3.8287706166 -2.8317014914 -0.1246297362
-3.0666715832 -2.9380464506 -0.9123594274
-4.5400698893 -2.0424996076 -0.4129879292
-4.3723844507 -3.7825268701 -0.0047853202
-4.3325401166 -2.3091472114
2.7110983045
-4.8826669039 -3.2632388353 2.7234694308
-5.0270594778 -1.4876749500 2.4779023036
-3.8921512031 -2.1208049280 3.7011069943
-4.7372107481
-4.4586942615
-5.4703866557
-1.1395664288 -0.0316616322
-2.2341513680 -0.8125844198
3.0197987441
2.4869361399
4.0099110077
6.2181959191
7.3037850000
6.0716615531
1.3824429899
1.3329155821
0.5220745953
-2.8761712214
1.1835147144
α-phosphonioallenyl complex [(triphos)(CO)2Re{C(PMePh2)=C=CPh(p-C6H4NO2)}]+ (6)
Re 1.829364 -1.005892 1.952043
C
O
C
O
2.297330 -2.859757 2.115316
2.721195 -3.957091 2.214157
1.864499 -0.805875 3.873872
1.926549 -0.659514 5.036754
C -1.335971 -0.479464 2.425926
C -2.341034 0.287987 2.878946
P
1.913597 -1.172453 -0.498017
28

H
P
H
H
P
H
C
H
H
C
H
H
C
H
H
C
H
2.644499 -2.322413 -0.921086
4.179541 -0.576400 1.840275
5.082235 -1.679388 1.897216
4.744090 0.179541 2.914096
1.882870 1.468852 1.798369
2.679064 1.931333 2.889384
2.915118 2.123138 0.356637
2.197122 2.616826 -0.321015
3.558815 2.924553 0.758168
4.844244 0.370469 0.359077
5.367729 -0.348994 -0.293536
5.605573 1.082393 0.719051
2.899428 0.186997 -1.347739
2.167005 0.799956 -1.901222
3.535120 -0.297051 -2.108599
3.760630 1.115435 -0.457806
4.323177 1.741245 -1.177755
C -2.471314 0.439583 4.367039
C -2.702385 0.643371 7.174331
C -1.388207 0.893236 5.145696
C -3.674576 0.087123 5.017254
C -3.787206 0.190303 6.408714
C -1.502666 0.992288 6.539234
H -0.458495 1.182448 4.647936
H -4.519466 -0.277853 4.424939
H -4.726479 -0.085972 6.898350
H -0.653021 1.351115 7.128569
C -3.322857 0.941365 1.982356
C -5.153713 2.215401 0.276096
C -4.211273 1.928797 2.472804
C -3.386069 0.614253 0.605429
C -4.290361 1.242857 -0.246472
C -5.125132 2.563912 1.629604
H -4.173263 2.212952 3.526806
H -2.712134 -0.149805 0.208409
H -4.356600 0.997083 -1.309036
H -5.810641 3.331362 1.996368
C
0.476895 -1.366935 -1.640408
C -1.726876 -1.658218 -3.382888
C -0.456289 -0.322443 -1.796428
C
0.295597 -2.558106 -2.372048
C -0.803380 -2.703049 -3.233410
C -1.545051 -0.463973 -2.667569
H -0.327655 0.617160 -1.248724
H
1.022428 -3.373242 -2.282197
H -0.926695 -3.630917 -3.800249
H -2.250674 0.363869 -2.790341
H -2.575808 -1.767067 -4.064008
C
0.581304 2.760759 1.904459
C -1.299655 4.848656 1.927954
C -0.531974 2.722555 1.044299
29

C
0.735546 3.844689 2.792161
C -0.205850 4.882365 2.803681
C -1.463768 3.767021 1.050291
H -0.689795 1.861091 0.387922
H
1.593774 3.883159 3.472077
H -0.080417 5.719752 3.496724
H -2.329142 3.724026 0.382547
H -2.030840 5.662448 1.935360
C -0.370151 -1.320032 2.092524
P -1.050422 -3.012870 2.189814
C -0.406967 -4.157567 0.913044
H -0.451238 -3.660681 -0.067809
H -1.050528 -5.050220 0.888387
H
0.628100 -4.451716 1.128795
N -6.101662 2.891644 -0.626748
O -6.848031 3.750655 -0.133156
O -6.083281 2.559137 -1.823982
H -2.794671 0.727439 8.261578
C -5.644465 -3.122374 1.530226
C -4.772493 -2.963831 0.442106
C -3.387570 -2.929433 0.645957
C -2.863498 -3.055406 1.951760
C -3.740499 -3.216286 3.041922
C -5.125892 -3.248037 2.826559
H -6.725635 -3.150362 1.366128
H -5.172620 -2.864991 -0.571370
H -2.722813 -2.801502 -0.214559
H -3.344341 -3.320776 4.056321
H -5.800832 -3.377725 3.678055
C -0.266766 -4.785989 6.394090
C -0.550974 -3.421352 6.239902
C -0.754218 -2.881626 4.963314
C -0.680248 -3.715899 3.827643
C -0.392540 -5.087718 3.984249
C -0.185413 -5.614965 5.265303
H -0.106235 -5.203924 7.392241
H -0.612186 -2.765572 7.113375
H -0.967547 -1.813809 4.856348
H -0.327771 -5.750488 3.116695
H
0.040499 -6.679131 5.379704
γ-phosphonioalkynyl complex [(triphos)(CO)2Re{C≡CCPh(p-C6H4NO2)(PMePh2)}]+ (5)
Re -4.315530 3.806255 4.592732
C -3.937995 4.197524 2.743347
O -3.698601 4.428024 1.615216
C -2.500164 4.244018 5.096249
O -1.398790 4.509906 5.402335
C -3.663563 1.866931 4.220855
C -3.172774 0.770815 3.889409
30