Activation of small molecules by phosphorus biradicaloids

Article abstract of DOI:10.1002/chem.201403964

The reactivity of biradicaloid [P(μ-NTer)] ₂ was employed to activate small molecules bearing single, double, and triple bonds. Addition of chalcogens (O₂, S₈, Se_x and Te_x) led to the formation of dic

Full text of DOI:10.1002/chem.201403964

Supporting Information
ꢀ
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014
Activation of Small Molecules by Phosphorus Biradicaloids
[a]
[a]
[b]
[a, b]
[a]
Alexander Hinz, Rene Kuzora, Uwe Rosenthal, Axel Schulz,*
and Alexander Villinger
chem_201403964_sm_miscellaneous_information.pdf

Supporting Information
Content
1
2
3
4
. Experimental ....................................................................................................................................... 2
. Structure Elucidation........................................................................................................................... 4
. Syntheses of compounds ................................................................................................................... 43
. References ......................................................................................................................................... 59
1

1
. Experimental
General Information. All manipulations were carried out under oxygen- and moisture-free
conditions under argon using standard Schlenk or drybox techniques.
Tetrahydrofuran (thf), benzene, toluene, diethylether were dried over Na/benzophenone, n-
hexane was dried over Na/benzophenone/tetraglyme. Acetonitrile and acetone were dried over
calcium hydride. All solvents were freshly distilled prior to use. [P(-NTer)]
NHyp)] , [ClP(-NDmp)] and [ClP(-NDipp)] were prepared according to literature
procedures.[1,2] Cp
Ti(btmsa), (Me Si)NSN(SiMe ), Ag(C )∙CH CN, and PhNCNPh were
prepared according to literature procedures.[3,4,5,9] Magnesium (99%, Merck) was stored under
Argon atmosphere and used as received. KMnO (98%, Merck), Sulphur (99%, Apolda),
Selenium (99%, Merck), Tellurium (99%, Alfa Aesar), and PhCCPh (99%, ABCR) were
used as received. CS (AlfaAesar) was desulfurized over Mercury and dried over P
distilled prior to use. Acetylene was consecutively dried over columns filled with KOH and
10 and was bubbled to toluene at –60 °C until saturation was achieved. The solution thus
obtained was stored at –80 °C until usage.
2
, [ClP(µ-
2
2
2
2
3
3
6
F
5
3
4
2
4
O10 and
4
P O
NMR: 29Si INEPT, 31P{ H}, F{ H}, C{ H}, 13C DEPT, 125Te and 77Se and H NMR
1
19
1
13
1
1
spectra were obtained on a Bruker Avance 250, 300 or 500 spectrometer and were referenced
1
3
internally to the deuterated solvents ( C, CD
2
Cl
2
: δreference = 54 ppm, C
H: δreference = 7.16 ppm)
PO4(aq), 19F: CFCl
) ).
6
D : δreference = 128
6
1
ppm) or to protic impurities ( H, CDHCl
2
: δreference = 5.32 ppm, C
6
D
5
1
25
, 77Se: SeMe2, 31P: 85 % H
, 29Si: Si(CH
or externally ( Te: Te(OH)
CD Cl was dried over P
prior to use.
6
3
3
3
4
2
2
4
O
10, C
6
D
6
was dried over Na/benzophenone and freshly distilled
IR: Nicolet 380 FT-IR with a Smart Orbit ATR device was used.
Raman: Bruker VERTEX 70 FT-IR with RAM II FT-Raman module, equipped with a
Nd:YAG laser (1064nm), or Horiba Scientific LabRam HR 800 were used.
CHN analyses: Analysator Flash EA 1112 from Thermo Quest, or C/H/N/S-Mikronalysator
TruSpec-932 from Leco were used.
Melting points are uncorrected (EZ-Melt, Stanford Research Systems). Heating-rate
2
0 °C/min (clearing-points are reported).
DSC: DSC 823e from Mettler-Toledo (Heating-rate 5 °C/min).
2

MS: Finnigan MAT 95-XP von Thermo Electron.
UV-VIS: Perkin Elmer Lambda 2 UV/VIS Spectrometer.
3

2
. Structure Elucidation
X-ray Structure Determination: X-ray quality crystals all compounds were selected in Kel-
F-oil (Riedel deHaen) or Fomblin YR-1800 perfluoroether (Alfa Aesar) at ambient
temperatures. The samples were cooled to 173(2) K during measurement. The data were
collected on a Bruker Apex Kappa-II CCD diffractometer using graphitemonochromated Mo
Kα radiation (λ = 0.71073). The structures were solved by direct methods (SHELXS-97)[6]
and refined by full-matrix least squares procedures (SHELXL-97).[7] Semi-empirical
absorption corrections were applied (SADABS).[8] All non hydrogen atoms were refined
anisotropically, hydrogen atoms were included in the refinement at calculated positions using
a riding model.
The P–(CS
The occupation of each part was refined freely (0.9269(1)/0.0731(1)). The P–((CH
unit in [P(-NTer)] ((CH CO) was found to be disordered and was split in two parts. The
occupation of each part was refined freely (0.620(3)/0.380(3)). The P–((CH
P(-NHyp)] ((CH
occupation of each part was refined freely (0.6822(1)/0.3178(1)). The P–(CH
P(-NHyp)] (CH
of each part was refined freely (0.770(5)/0.230(5)). One Et
NTer)] (S(NSiMe ) was found to be disordered and was split in two parts. The occupation
of each part was refined freely (0.729(5)/0.271(5)). All (C )P units in [(C )P(-NTer)]
2
)–P unit in [P(-NTer)]
2
CS
2
was found to be disordered and was split in two parts.
)
3 2
CO)–P
2
)
3 2
3
)
2
CO)–P unit in
CN)–P unit in
[
2
3
)
2
CO) was found to be disordered and was split in two parts. The
3
[
2
3
CN) was found to be disordered and was split in two parts. The occupation
O solvent molecule in [P(-
2
2
)
3 2
6
F
5
6
F
5
2
was found to be disordered and was split in two parts. The occupation of each part was
refined freely (0.790(1)/0.210(1), 0.616(1)/ 0.384(1)). The cocrystallised molecule of n-
hexane was found to be disordered and split into two parts. The occupation of each part was
refined freely (0.661(2)/0.339(2)). A Mes*NP moiety of Mes*
disordered and split into two parts. The occupation of both parts was refined freely
0.894(6)/0.106(6)). The phenyl group in [P(-NTer)] (PhCCPh) was found to be disordered
and split into two parts. The occupation of both parts was refined freely (0.517(8)/0.483(8)).
Both symmetry independent molecules of [P(-NTer)] (PhNCNPh) in the asymmetric unit
3
N
3
2
P was found to be
(
2
2
were found to possess disordered P–(PhNCNPh)–P units. Each was split into two parts whose
occupation was allowed to refine freely (0.876(1)/0.124(1) and 0.951(1)/0.049(1),
respectively). Cocrystallised molecules of the solvent, toluene, were found to be heavily
4

disordered and removed from the model using the PLATON program and its SQUEEZE
feature.
5

Table S1. Crystallographic details of β-P
4
(NDmp)
4
, Cp
2
Ti[P(NDipp)
2
]
2
and [P(-
NTer)]
2
2
O .
4
6
Cp
β-P
4
(NDmp)
4
2
Ti[P(NDipp)
2
]
2
Mes*
3
N P
3 2
Chem. formula
C
32
H
36
4
N P
4
C
34
H
44
2
N PTi
C54 H87 N3 P2
840.21
-1
Form. wght. [g mol ]
Colour
600.53
yellow
559.58
yellow
red
Cryst. system
Space group
monoclinic
P2 /c
triclinic
orthorhombic
Pbcn
1
P-1
a [Å]
b [Å]
c [Å]
15.3713(6)
9.9893(4)
20.3793(9)
10.4438(6)
16.5835(9)
19.7588(1)
28.416(1)
9.5983(5)
38.295(2)
α [°]
90
68.597(3)
89.014(3)
79.629(3)
90
90
90


[°]
[°]
103.457(2)
9
0
3
V [Å ]
3043.3(2)
4
3129.7(3)
4
10444.7(8)
8
Z
-3


calc. [g cm ]
1.311
0.28
1.188
0.35
1.069
0.119
0.71073
173
-1
[mm ]
λMoKα [Å]
0.71073
173
0.71073
173
T [K]
Measured reflections
36100
7671
55489
12374
7626
0.067
1196
0.047
0.108
1.01
64730
11406
6457
Independent reflections
Reflections with I > 2σ(I) 4311
R
int.
0.078
1264
0.052
0.127
0.958
369
0.09
F(000)
3696
2
2
R
1
(R [F > 2σ(F )])
0.055
0.139
1.013
651
wR (all data)
2
GooF
Parameters
CCDC #
701
6

Table S1. Crystallographic details of β-P
4
(NDmp)
4
, Cp
2
Ti[P(NDipp)
2
]
2
and [P(-
NTer)]
2
2
O .
8
O
2
8O
2
∙ 0.5 C
6
H
6
8S
2
[
P(-NTer)]
2
O
2
[P(-NTer)]
2
O
2
[P(-NTer)]
2 2
S
Chem. formula
C
48
H
50
2
N P
2
O
2
C
48
H
50
2
N P
2
O
2
C
48
H
50
2
N P
S
2 2
∙
0.25 (C
6
6
H )
-1
Form. wght. [g mol ]
Colour
748.84
yellow
1536.73
yellow
triclinic
P-1
780.96
yellow
Cryst. system
Space group
monoclinic
P2 /c
monoclinic
P2 /n
1
1
a [Å]
b [Å]
c [Å]
10.7419(3)
15.3547(5)
24.7274(7)
12.8161(8)
15.3259(9)
21.484(1)
12.6318(5)
21.0205(8)
16.0688(7)
α [°]
90
95.865(2)
88.717(4)
89.674(4)
89.736(4)
90


[°]
[°]
106.723(2)
90
9
0
3
V [Å ]
4057.2(2)
4
4218.6(4)
4
4086.2(3)
4
Z
-3


calc. [g cm ]
1.226
0.15
1.210
0.145
0.71073
173
1.269
0.25
-1
[mm ]
λMoKα [Å]
0.71073
173
0.71073
173
T [K]
Measured reflections
65703
14034
84563
19304
9248
53511
9856
7215
0.067
1656
0.048
0.133
1.024
500
Independent reflections
Reflections with I > 2σ(I) 9583
R
int.
0.060
1592
0.047
0.130
1.015
499
0.100
1634
F(000)
2
2
R
1
(R [F > 2σ(F )])
0.059
0.148
0.994
1026
wR (all data)
2
GooF
Parameters
CCDC #
7

Table S2. Crystallographic details of [P(-NTer)]
2
S
2
, [P(-NTer)]
2
Se
2
and [P(-
NTer)] Te
2
2
.
8
Se
2
8Te
2
9
[
P(-NTer)]
2
Se
2
[P(-NTer)]
2
Te
2
[P(-NTer)]
2
(
H
2
CCH
2
)
Chem. formula
C
48
H
50
2
N P
Se
2 2
C
48
H
50
2
N P
2
Te
2
C
50
H
54
N P
2 2
·
(C
1058.21
dark green
monoclinic
P2 /c
6
H
14
)
-1
Form. wght. [g mol ]
Colour
874.76
orange
744.89
colourless
monoclinic
P2 /n
Cryst. system
Space group
monoclinic
P2 /n
1
1
1
a [Å]
b [Å]
c [Å]
12.7117(5)
20.9924(9)
16.1587(6)
12.5213(8)
23.4301(1)
16.8909(9)
12.599(1)
21.062(2)
15.989(2)
α [°]
90
90
90


[°]
[°]
106.168(2)
90.927(3)
90
107.039(4)
90
9
0
3
V [Å ]
4141.4(3)
4
4954.7(5)
4
4056.5(6)
4
Z
-3


calc. [g cm ]
1.403
1.90
1.419
1.28
1.220
0.145
0.71073
173
-1
[mm ]
λMoKα [Å]
0.71073
173
0.71073
193
T [K]
Measured reflections
54560
12061
43998
9204
6131
0.074
2144
0.057
0.149
1.035
554
33263
9323
4915
0.088
1592
0.056
0.149
1.005
503
Independent reflections
Reflections with I > 2σ(I) 8982
R
int.
0.050
1800
0.040
0.105
1.052
499
F(000)
2
2
R
1
(R [F > 2σ(F )])
wR (all data)
2
GooF
Parameters
CCDC #
8

Table S3. Crystallographic details of [P(-NTer)]
NHyp)] ((CH CO).
2
CS
11
2
, [P(-NTer)]
2
((CH
3
) CO) and [P(-
2
2
)
3 2
1
0
11Hyp
[
P(-NTer)]
2
CS
2
[P(-NTer)]
(CH CO)
2
[P(-NHyp)]
2
(
3
)
2
((CH
3
)
2
CO)
Chem. formula
C
49
H
50
P
2
2
N S
2
C
51
H
56
N
2
P
2
O
C
21
H
60
N
2
OP
2
Si
8
-1
Form. wght. [g mol ]
Colour
792.97
green
774.92
colourless
643.37
yellow
Cryst. system
Space group
monoclinic
P2 /n
orthorhombic
monoclinic
P2 /c
1
Pbca
1
a [Å]
b [Å]
c [Å]
12.5814(6)
21.2606(1)
16.2114(8)
22.8742(9)
15.3061(7)
24.7109(1)
16.5810(8)
18.3811(1)
13.4374(6)
α [°]
90
90
90
90
90


[°]
[°]
106.038(2)
105.686(2)
90
9
0
3
V [Å ]
4167.6(3)
4
8651.7(6)
8
3942.9(3)
4
Z
-3


calc. [g cm ]
1.264
0.24
1.190
0.14
1.084
0.37
-1
[mm ]
λ
MoKα [Å]
0.71073
173
0.71073
173
0.71073
173
T [K]
Measured reflections
44823
9470
61137
10887
6899
0.058
3312
0.051
0.139
1.046
570
66010
12555
8660
0.058
1400
0.043
0.109
1.058
403
Independent reflections
Reflections with I > 2σ(I) 5576
R
int.
0.068
1680
0.061
0.150
1.024
525
F(000)
2
2
R
1
(R [F > 2σ(F )])
wR (all data)
2
GooF
Parameters
CCDC #
9

Table S4. Crystallographic details of [P(-NTer)]
(C )P(-NTer)]
2
(CH
13
3
CN), [P(-NTer)]
2
(S(NSiMe
3
2
) ) and
[
6
F
5
2
.
1
2
14
[
(
P(-NTer)]
S(NSiMe
2
[P(-NTer)]
(PhNCNPh)
2
[P(-NTer)]
2
3
)
2
)
(CH CN)
3
Chem. formula
C
54
H
69
4
N P
2
SSi
2
C
61
H
60
4
N P
2
C
50
H
53
N P
3 2
·
2 (C
4
H
10O)
· 1.125 (C
1014.72
colourless
triclinic
P-1
7
8
H )
-1
Form. wght. [g mol ]
Colour
1072.55
757.89
yellow
colourless
Cryst. system
Space group
monoclinic
monoclinic
P2 /n
P2
1
/c
1
a [Å]
b [Å]
c [Å]
14.9697(4)
11.9960(3)
34.4792(9)
11.7212(4)
20.7236(8)
23.880(1)
12.6279(4)
21.1223(6)
16.1140(6)
α [°]
90
104.108(2)
95.184(2)
95.184(2)
90


[°]
[°]
95.5380(10)
106.055(2)
90
9
0
3
V [Å ]
6162.8(3)
4
5560.9(4)
4
4130.5(2)
4
Z
-3


calc. [g cm ]
1.156
0.19
1.212
0.125
0.71073
173
1.219
0.14
-1
[mm ]
λMoKα [Å]
0.71073
173
0.71073
173
T [K]
Measured reflections
90953
17951
163748
35287
21229
0.055
2161
45174
8564
5084
0.074
1616
0.059
0.156
1.032
547
Independent reflections
Reflections with I > 2σ(I) 13139
R
int.
0.059
2316
0.050
0.135
1.036
708
F(000)
2
2
R
1
(R [F > 2σ(F )])
0.061
0.149
1.024
1317
wR (all data)
2
GooF
Parameters
CCDC #
1
0

Table S5. Crystallographic details of [P(-NTer)]
NTer)] (PhNCNPh).
2
(PhCCPh) and [P(-
2
1
5H
15Ph
[
P(-NTer)]
2
[P(-NTer)]
2
(HCCH)
(PhCCPh)
Chem. formula
C
50
H
52
2
N P
2
C
60
H
60
N P
2 2
-1
Form. wght. [g mol ]
Colour
742.88
colourless
monoclinic
P2 /n
895.06
yellow
Cryst. system
Space group
monoclinic
1
C2/c
a [Å]
b [Å]
c [Å]
12.5531(5)
21.0733(8)
15.9788(6)
17.968(2)
11.3732 (1)
23.893 (2)
α [°]
90
90


[°]
[°]
106.707(2)
98.566 (4)
90
9
0
3
V [Å ]
4048.5(3)
4
4828.2 (8)
4
Z
-3


calc. [g cm ]
1.219
0.145
0.71073
173
1.231
0.133
0.71073
173
-1
[mm ]
λMoKα [Å]
T [K]
Measured reflections
58209
11815
43213
8719
7185
0.040
1904
0.044
0.128
1.042
320
Independent reflections
Reflections with I > 2σ(I) 7460
R
int.
0.065
1584
0.052
0.140
1.026
507
F(000)
2
2
R
1
(R [F > 2σ(F )])
wR (all data)
2
GooF
Parameters
CCDC #
1
1

Scheme S1. Numbering scheme of β-P
4
(NDmp) (4).
4
Table S6. Selected bond lengths (Å) and angles (°) of β-P
4
(NDmp) .
4
P1—N4
P1—P2
P1—P3
P2—N1
P2—N2
P3—N3
P3—N1
P4—N3
P4—N4
P4—N2
N1—C1
N2—C9
1.708(2)
2.2558(9)
2.2858(10)
1.719(2)
1.721(2)
1.7227(19)
1.730(2)
1.726(2)
1.731(2)
1.7315(18)
1.441(3)
1.460(3)
N3—C17
N4—C25
1.450(3)
1.456(3)
82.19(8)
96.97(7)
96.54(8)
75.72(3)
105.64(10)
83.34(7)
93.18(7)
105.85(9)
92.68(7)
96.64(10)
N1—P3—P1
N4—P1—P2
N4—P1—P3
P2—P1—P3
N1—P2—N2
N1—P2—P1
N2—P2—P1
N3—P3—N1
N3—P3—P1
N3—P4—N4
1
2

N3—P4—N2
99.24(9)
P2—P1—P3—N3
N4—P1—P3—N1
P2—P1—P3—N1
N2—P2—N1—P3
P1—P2—N1—P3
N3—P3—N1—P2
P1—P3—N1—P2
N1—P2—N2—P4
P1—P2—N2—P4
N3—P4—N2—P2
N4—P4—N2—P2
N1—P3—N3—P4
P1—P3—N3—P4
N4—P4—N3—P3
N2—P4—N3—P3
P2—P1—N4—P4
P3—P1—N4—P4
N3—P4—N4—P1
N2—P4—N4—P1
84.64(7)
N4—P4—N2
96.27(9)
−116.55(10)
−21.00(7)
62.50(13)
−28.95(9)
−61.97(13)
28.61(9)
C1—N1—P2
123.26(16)
128.30(16)
107.86(11)
120.02(15)
117.56(15)
118.71(10)
120.63(15)
119.97(15)
119.02(11)
123.65(15)
124.08(16)
111.83(11)
−10.92(9)
116.10(10)
21.09(7)
C1—N1—P3
P2—N1—P3
C9—N2—P2
C9—N2—P4
P2—N2—P4
−64.28(14)
19.69(12)
55.57(14)
−42.23(14)
63.01(14)
−19.63(11)
42.49(13)
−55.00(13)
−38.09(11)
38.26(11)
−50.29(12)
49.81(13)
C17—N3—P3
C17—N3—P4
P3—N3—P4
C25—N4—P1
C25—N4—P4
P1—N4—P4
N4—P1—P3—N3
N4—P1—P2—N1
P3—P1—P2—N1
N4—P1—P2—N2
P3—P1—P2—N2
10.71(10)
−84.30(7)
1
3

Scheme S2. Numbering scheme of Cp
2
Ti[P(NDipp)
2
2
] (6).
Table S7. Selected bond lengths (Å) and angles (°) of Cp
2
Ti[P(NDipp)
2
2
] .
P1—N1
P1—N2
P1—Ti1
Ti1—N2
Ti1—N1
N1—C1
N2—C13
P2—N4
P2—N3
P2—Ti2
Ti2—N3
Ti2—N4
1.6008(18)
1.6040(19)
2.9555(7)
2.2652(18)
2.2959(18)
1.432(3)
N4—C47
1.440(3)
N1—P1—N2
N2—Ti1—N1
C1—N1—P1
C1—N1—Ti1
P1—N1—Ti1
C13—N2—P1
C13—N2—Ti1
P1—N2—Ti1
N4—P2—N3
N3—Ti2—N4
C35—N3—P2
99.79(9)
65.01(6)
119.99(14)
141.85(14)
97.04(8)
1.429(3)
122.51(15)
137.78(15)
98.16(9)
1.5988(19)
1.6058(19)
2.9612(8)
2.2758(18)
2.2946(18)
99.74(10)
64.83(6)
119.65(15)
1
4

N3—C35
1.437(3)
C35—N3—Ti2
140.51(14)
83.5(2)
P2—N3—Ti2
97.95(9)
C29—Ti1—N2—C13
N1—Ti1—N2—P1
N4—P2—N3—C35
N4—P2—N3—Ti2
N4—Ti2—N3—C35
N4—Ti2—N3—P2
N3—P2—N4—C47
Ti2—P2—N4—C47
N3—P2—N4—Ti2
N3—Ti2—N4—C47
N3—Ti2—N4—P2
C47—N4—P2
119.35(15)
142.44(14)
97.42(9)
−0.07(7)
−165.39(17)
2.08(10)
C47—N4—Ti2
P2—N4—Ti2
N2—P1—N1—C1
N2—P1—N1—Ti1
N2—Ti1—N1—C1
N2—Ti1—N1—P1
N1—P1—N2—C13
Ti1—P1—N2—C13
C25—Ti1—N2—C13
−170.57(16)
−0.09(9)
166.7(2)
161.2(3)
−1.58(7)
−174.13(16)
−172.1(2)
−2.06(10)
170.2(3)
0.07(7)
−168.01(17)
−168.1(2)
77.4(2)
1.59(7)
1
5

Scheme S3. Numbering scheme of Mes*
3
N
3
2
P .
C52A
C53A
C49A
C47A
C50A
C48A
C51A
4
C
1A
40A
C
C54A
C8
C9
C10
C42A
C37A
N2A
C39A
C38A
C7
C12A
C13A
C3
C2
C46A
C43A
C11 C4
C1
N1
C45A
P2A
C14A
C44A
C36
C35
C5
C6
P1
N2
C18
C34
C15
C33
C16
17C
C19 C24
C25 C20 C23
C21 C22
C29
C31
C26
C27
28C
C32
C30
Table S8. Selected bond lengths (Å) and angles (°) of Cp
2
Ti[P(NDipp)
2
2
] .
P1–N1
1.535(2)
1.706 (2)
1.415(3)
1.465(3)
1.746(2)
1.76(2)
P2A–N3A
1.534(3)
1.418(3)
1.53(1)
P1–N2
N3A–C37A
P2B–N3B
N1–C1
N2–C19
N2–P2A
N2–P2B
C19–N2–P1
P1–N2–P2A
N3B–C37B
N1–P1–N2
C1–N1–P1
C19–N2–P2A
C19–N2–P2B
1.424(9)
106.1(1)
140.8(2)
128.3(2)
119.2(5)
114.1(2)
117.4(1)
1
6

P1–N2–P2B
123.6(5)
108.4(2)
112(1)
P2A–N2–P2B
14.0(5)
N3A–P2A–N2
C37A–N3A–P2A
C37B–N3B–P2B
N1–P1–N2–C19
N1–P1–N2–P2B
P1–N2–P2A–N3A
P2A–N3A–C37A–C38A
137.5(3)
135(2)
N3B–P2B–N2
N2–P1–N1–C1
N1–P1–N2–P2A
C19–N2–P2A–N3A
N2–P2A–N3A–C37A
178.9(2)
6.0(2)
–179.5(2)
20.7(6)
9.4(3)
–177.1(3)
162.4(6)
–174.1(6)
1
7

Scheme S4. Numbering scheme of [P(-NTer)]
2
O
2
(8O ).
2
Table S9. Selected bond lengths (Å) and angles (°) of [P(µ-NTer)]
2
2
O .
P1—N2
1.6432(11)
1.6450(11)
1.4606(12)
2.5811(5)
1.7986(11)
1.7980(12)
1.4587(12)
1.4315(14)
1.4314(15)
127.02(9)
132.19(9)
127.34(9)
C25—N2—P2
O1—P2—P1
O2—P2—P1
N2—P1—N1
N2—P2—N1
O1—P2—N2
O2—P2—N2
O1—P2—N1
O2—P2—N1
O2—P2—O1
P1—N1—P2
P1—N2—P2
129.17(9)
116.90(5)
116.76(5)
87.49(5)
78.42(5)
114.17(6)
106.36(6)
106.84(6)
114.72(6)
126.34(7)
97.00(5)
97.09(5)
P1—N1
P2—O1
P1—P2
P2—N1
P2—N2
P2—O2
N1—C1
N2—C25
C1—N1—P1
C1—N1—P2
C25—N2—P1
1
8

N2—P1—P2—O2
N1—P1—P2—O2
N2—P1—P2—O1
N1—P1—P2—O1
N1—P1—P2—N2
N2—P1—P2—N1
N2—P1—N1—C1
P2—P1—N1—C1
N2—P1—N1—P2
O2—P2—N1—C1
O1—P2—N1—C1
N2—P2—N1—C1
P1—P2—N1—C1
−83.14(8)
97.06(8)
O2—P2—N1—P1
O1—P2—N1—P1
N2—P2—N1—P1
N1—P1—N2—C25
P2—P1—N2—C25
N1—P1—N2—P2
O2—P2—N2—C25
O1—P2—N2—C25
N1—P2—N2—C25
P1—P2—N2—C25
O2—P2—N2—P1
O1—P2—N2—P1
N1—P2—N2—P1
−102.71(7)
112.13(7)
0.13(6)
95.98(8)
−83.82(8)
−179.80(9)
179.80(9)
159.91(12)
160.04(14)
−0.14(6)
153.68(12)
153.55(14)
0.14(6)
−40.32(13)
103.63(12)
−152.95(12)
−152.82(15)
112.50(6)
−103.55(7)
−0.13(6)
98.87(13)
−46.29(14)
−158.29(13)
−158.42(16)
1
9

Scheme S5. Numbering scheme of [P(-NTer)]
2
O
2
(8O
2
∙ 0.25 C
6
6
H ).
C14
C47
C44
C11 C10
C43 C42
C15
C12
C7
C9
C41 C46
C8
C45 C40
O1
N1
O2
C3
C2
C13
C24
C48
C30 C29
P1
C4
C1
N2
C25
C28
P2
C5
C6
C37
C26 C27
C16 C21
C17 C20
C18 C19
C32 C31
C33
C34 C35
C22
C36 C39
C23
C38
C97
C99'
C98'
C98
C99
C
C62
C57
C95
9
7'
C59 C58
C91 C90
C92
C93 C88
C63
C60
C55 C56
C51 C50
C52 C49
C53 C54
C64 C69
C65 C68
C66 C67
C71
C89 C94
O3
O4
C61
C72
C96
C78 C77
P3
P4
N3
N4
C73
C76
C85
C74 C75
C80 C79
C81
C82 C83
C86
C70
C84 C87
Symmetry code: (‘) 1-x, -y, 1-z
2
0

Table S10. Selected bond lengths (Å) and angles (°) of [P(µ-NTer)]
2
O
2
∙ 0.25 C
6
6
H .
P1–O1
1.4609(19)
1.4615(18)
1.786(2)
P3–O3
1.459(2)
P1–O2
P3–O4
1.4587(19)
1.786(2)
P1–N1
P3–N4
P1–N2
1.792(2)
P3–N3
1.792(2)
P1–P2
2.5853(10)
1.645(2)
P3–P4
2.5844(10)
1.643(2)
P2–N2
P4–N4
P2–N1
1.653(2)
P4–N3
1.644(2)
N1–C1
1.439(3)
N3–C49
1.429(3)
N2–C25
1.436(3)
N4–C73
1.432(3)
O1–P1–O2
O1–P1–N1
O2–P1–N1
O1–P1–N2
O2–P1–N2
N1–P1–N2
O1–P1–P2
O2–P1–P2
N2–P2–N1
O1–P1–P2–N2
O2–P1–P2–N2
N1–P1–P2–N2
125.72(11)
107.06(10)
114.61(11)
114.57(11)
106.74(10)
78.45(10)
117.30(8)
116.98(8)
86.64(10)
96.13(14)
–83.47(14)
179.87(16)
O3–P3–O4
O3–P3–N4
O4–P3–N4
O3–P3–N3
O4–P3–N3
N4–P3–N3
O3–P3–P4
O4–P3–P4
N4–P4–N3
O3–P3–P4–N4
O4–P3–P4–N4
N3–P3–P4–N4
125.66(12)
106.97(11)
115.10(12)
114.58(11)
106.62(11)
78.15(10)
117.53(8)
116.81(9)
86.68(11)
–83.10(15)
97.55(15)
–178.98(16)
2
1

Scheme S6. Numbering scheme of [P(µ-NTer)]
2
S
2
(8S ).
2
Table S11. Selected bond lengths (Å) and angles (°)of [P(µ-NTer)]
2
2
S .
P1—N2
P1—N1
P1—S1
1.7066(17)
1.7689(16)
2.1755(8)
2.5557(7)
1.7288(16)
1.7328(17)
2.1774(9)
2.0752(10)
1.422(2)
C1—N1—P2
C24—N2—P1
C24—N2—P2
N2—P1—N1
N2—P1—S1
N1—P1—S1
S2—P2—P1
N2—P2—N1
N1—P2—S2
N2—P2—S2
S1—P1—P2
129.55(13)
133.96(13)
129.30(13)
80.14(7)
P1—P2
P2—N2
P2—N1
P2—S2
100.19(6)
93.89(6)
83.07(3)
80.55(8)
97.02(6)
95.89(6)
83.99(3)
S1—S2
N1—C1
N2—C25
C1—N1—P1
1.422(2)
124.36(13)
2
2

S2—S1—P1
95.66(3)
P1—P2—S2—S1
P1—P2—N1—C1
N2—P2—N1—P1
S2—P2—N1—P1
N2—P1—N1—C1
S1—P1—N1—C1
P2—P1—N1—C1
N2—P1—N1—P2
S1—P1—N1—P2
N1—P1—N2—C25
S1—P1—N2—C25
P2—P1—N2—C25
N1—P1—N2—P2
S1—P1—N2—P2
N1—P2—N2—C25
S2—P2—N2—C25
P1—P2—N2—C25
N1—P2—N2—P1
S2—P2—N2—P1
5.62(3)
S1—S2—P2
96.69(3)
−142.0(2)
−22.58(8)
72.25(6)
P2—N1—P1
93.74(8)
P1—N2—P2
96.13(8)
N2—P2—N1—C1
S2—P2—N1—C1
N2—P1—P2—N1
S1—P1—P2—N1
N1—P1—P2—N2
S1—P1—P2—N2
N2—P1—P2—S2
N1—P1—P2—S2
S1—P1—P2—S2
N2—P1—S1—S2
N1—P1—S1—S2
P2—P1—S1—S2
P1—S1—S2—P2
N1—P2—S2—S1
N2—P2—S2—S1
−164.53(17)
−69.70(16)
−145.21(12)
102.43(8)
145.21(12)
−112.35(9)
107.00(9)
−107.78(8)
−5.35(3)
167.78(16)
68.09(15)
144.85(19)
22.92(8)
−76.76(7)
165.65(19)
−102.14(18)
−171.3(2)
−23.07(8)
69.15(7)
−33.60(6)
47.07(6)
−164.56(18)
99.28(16)
171.9(2)
5.60(3)
−6.59(3)
−35.89(6)
45.28(6)
23.54(8)
−72.62(7)
2
3

Scheme S7. Numbering scheme of [P(µ-NTer)]
2
Se
2
(8Se ).
2
Table S12. Selected bond lengths (Å) and angles (°) of [P(µ-NTer)]
2
Se .
2
P1—N2
1.7107(15)
1.7659(16)
2.3323(5)
2.5758(7)
1.7290(15)
1.7272(16)
2.3327(6)
2.3314(4)
1.418(2)
C25—N2—P1
C25—N2—P2
N2—P1—N1
N2—P1—Se1
N1—P1—Se1
Se2—P2—P1
N2—P2—N1
N1—P2—Se2
N2—P2—Se2
Se1—P1—P2
Se2—Se1—P1
Se1—Se2—P2
134.06(13)
128.67(12)
80.27(7)
P1—N1
P1—Se1
P1—P2
101.31(6)
94.40(5)
P2—N1
P2—N2
86.26(2)
P2—Se2
Se1—Se2
N1—C1
80.86(7)
98.19(5)
96.11(6)
N2—C25
C1—N1—P2
C1—N1—P1
1.419(2)
87.35(2)
129.85(13)
125.32(12)
92.202(15)
93.381(15)
2
4

P2—N1—P1
94.95(7)
P1—P2—N1—C1
N2—P2—N1—P1
Se2—P2—N1—P1
N2—P1—N1—C1
Se1—P1—N1—C1
P2—P1—N1—C1
N2—P1—N1—P2
Se1—P1—N1—P2
N1—P1—N2—C25
Se1—P1—N2—C25
P2—P1—N2—C25
N1—P1—N2—P2
Se1—P1—N2—P2
N1—P2—N2—C25
Se2—P2—N2—C25
P1—P2—N2—C25
N1—P2—N2—P1
Se2—P2—N2—P1
−145.90(19)
−19.42(7)
75.50(6)
P1—N2—P2
97.04(8)
N2—P2—N1—C1
Se2—P2—N1—C1
N2—P1—P2—N1
Se1—P1—P2—N1
N1—P1—P2—N2
Se1—P1—P2—N2
N2—P1—P2—Se2
N1—P1—P2—Se2
Se1—P1—P2—Se2
N2—P1—Se1—Se2
N1—P1—Se1—Se2
P2—P1—Se1—Se2
P1—Se1—Se2—P2
N1—P2—Se2—Se1
N2—P2—Se2—Se1
P1—P2—Se2—Se1
−165.32(17)
−70.40(16)
−150.13(11)
99.57(8)
167.82(16)
67.08(14)
148.17(18)
19.65(7)
150.13(11)
−110.29(8)
103.67(8)
−106.19(8)
−6.621(17)
−32.92(6)
48.02(5)
−81.09(6)
165.58(18)
−101.84(17)
−174.7(2)
−19.75(7)
72.84(7)
6.615(17)
−7.313(19)
−34.88(5)
46.73(5)
−164.75(16)
97.90(15)
175.1(2)
20.15(8)
6.628(17)
−77.20(6)
2
5

Scheme S8. Numbering scheme of [P(µ-NTer)]
2
Te
2
·(C
6
H
14) (8Te ).
2
C38
C14
C10
C33
C32
C9
C34
C35
C8
C37
C11
C15
C49
C7
C31
C36
C39
C12
C13
(
Te
2)
C27 C26
(
P
2)
C2
C3
C50
C1
C51
C28
N
2)
N
C4
C25
C40
(1)
C24
(
P
(1)
C52
C53
C48
C45
C29 C30
C41
C6
C5
Te
(1)
C16
C53
C21
C20
C19
C17
C46
C44
C43
C22
C42
C18
C47
C23
Table S13. Selected bond lengths (Å) and angles (°) of [P(µ-NTer)]
2
Te
2
·(C H14).
6
P1—N1
P1—N2
Te1—P1
P1—P2
1.704(5)
1.746(5)
2.6003(19)
2.600(2)
1.720(6)
1.752(5)
2.6137(18)
2.6853(9)
1.412(8)
1.415(8)
C25—N2—P2
C25—N2—P1
N1—P1—N2
N2—P1—Te1
N1—P1—Te1
P1—P2—Te2
N2—P2—N1
N1—P2—Te2
N2—P2—Te2
P2—P1—Te1
133.1(4)
128.6(4)
80.8(2)
94.40(17)
101.89(18)
90.29(7)
80.2(2)
P2—N2
P2—N1
Te2—P2
Te1—Te2
N1—C1
N2—C25
93.79(17)
102.32(18)
90.36(7)
2
6

C1—N1—P1
132.6(4)
127.7(4)
97.6(3)
P1—Te1—Te2
88.71(4)
88.21(4)
86.8(5)
C1—N1—P2
P2—Te2—Te1
P1—N1—P2
Te1—P1—N1—C1
N2—P1—N1—P2
Te1—P1—N1—P2
N2—P2—N1—C1
P1—P2—N1—C1
Te2—P2—N1—C1
N2—P2—N1—P1
Te2—P2—N1—P1
N1—P2—N2—C25
P1—P2—N2—C25
Te2—P2—N2—C25
N1—P2—N2—P1
Te2—P2—N2—P1
N1—P1—N2—C25
P2—P1—N2—C25
Te1—P1—N2—C25
N1—P1—N2—P2
Te1—P1—N2—P2
P2—N2—P1
97.2(3)
15.6(2)
P1—Te1—Te2—P2
Te2—Te1—P1—N1
Te2—Te1—P1—N2
Te2—Te1—P1—P2
N1—P1—P2—N2
Te1—P1—P2—N2
N2—P1—P2—N1
Te1—P1—P2—N1
N1—P1—P2—Te2
N2—P1—P2—Te2
Te1—P1—P2—Te2
Te1—Te2—P2—N2
Te1—Te2—P2—N1
Te1—Te2—P2—P1
N2—P1—N1—C1
P2—P1—N1—C1
11.67(5)
28.88(17)
−52.61(19)
−11.73(5)
156.2(4)
−96.3(3)
−156.2(4)
107.6(3)
−95.5 (3)
108.3(3)
12.05(6)
28.66(17)
−52.08(18)
−11.67(5)
179.4(6)
163.8(7)
−77.0(2)
179.2(5)
−164.9(6)
−78.9(5)
−15.9(2)
86.0(2)
−175.8(6)
168.7(7)
92.4(5)
15.5(2)
−76.3(2)
174.6(5)
−169.5(6)
−84.0(5)
−15.9(2)
85.5(2)
2
7

Scheme S9. Numbering scheme of [P(µ-NTer)]
2
(H
2
CCH ) (9).
2
C16
C13 C12
C14 C11
C9 C10
C15
N1
C26
C18 C23
C19 C22
C20 C21
C25
C49
C45 C44
C17
C46
C43 C48
C47 C42
C5
C4
C8
C50
C32 C31
P1
P2
C1
N2
C2
C6
C3
C27
C30
C7
C39
C28 C29
C34 C33
C35
C36 C37
C40
C24
C38 C41
Table S14. Selected bond lengths (Å) and angles (°) of [P(µ-NTer)]
2
(H
2
CCH ).
2
P1—N2
1.715(2)
1.787(2)
1.870(3)
2.5316(10)
1.741(2)
1.758(2)
1.863(3)
1.520(4)
93.29(7)
-5.52(14)
-9.2(2)
N2—P1—N1
N2—P1—C1
N1—P1—C1
C1—P1—P2
N2—P2—N1
N2—P2—C2
C2—P2—P1
P2—N1—P1
P1—N2—P2
C2—C1—P1
C1—C2—P2
79.99(9)
P1—N1
95.29(12)
89.82(11)
74.25(10)
80.09(9)
P1—C1
P1—P2
P2—N2
P2—N1
91.38(11)
73.98(9)
P2—C2
C1—C2
91.13(9)
P2—N2—P1
C1—P1—P2—C2
P1—C1—C2—P2
94.18(10)
105.00(18)
105.93(18)
2
8

Scheme S10. Numbering scheme of [P(µ-NTer)]
2
CS (10).
2
Table S15. Selected bond lengths (Å) and angles (°) of [P(µ-NTer)]
2
CS .
2
N1—C1
1.426(3)
1.452(15)
1.737(3)
1.760(12)
1.777(2)
1.418(3)
1.721(2)
1.721(2)
1.752(16)
1.919(13)
2.2450(16)
P1A—P2A
2.5441(12)
1.915(4)
1.721(4)
1.610(3)
2.251(9)
2.551(9)
1.920(10)
1.706(10)
1.606(9)
127.4(7)
131.3(2)
N1—P2B
N1—P1A
N1—P1B
N1—P2A
N2—C25
N2—P2A
N2—P1A
N2—P2B
N2—P1B
P1A—S1A
P2A—C49A
S1A—C49A
S2A—C49A
P1B—S1B
P1B—P2B
P2B—C49B
S1B—C49B
S2B—C49B
C1—N1—P2B
C1—N1—P1A
2
9